Paul Laurence Dunbar Chambers Jr. was born in Pittsburgh on April 22, 1935, and named after the poet. After his mother's death in 1948 he moved to Detroit to live with his father, arriving in a city whose public school music program was about to produce a generation of major jazz musicians. He started on baritone horn, switched to tuba, and took up the double bass around 1949. Formal study began in 1952 with Gaston Brohan, principal bassist of the Detroit Symphony Orchestra, and Chambers enrolled at Cass Technical High School, playing in the school symphony while working the city's clubs at night. He sat in at the Blue Bird Inn, Klein's Show Bar, and the Rouge Lounge alongside Thad Jones and Kenny Burrell, and learned harmony and walking-line construction at after-hours sessions in the homes of pianists Barry Harris and Hugh Lawson. The bassists he studied were Oscar Pettiford, Ray Brown, Percy Heath, Milt Hinton, Wendell Marshall, Charles Mingus, and George Duvivier, with Duke Ellington's Jimmy Blanton his stated favorite. In 1952 he married Ann Williams, introduced to him by his close friend and fellow Detroit bassist Doug Watkins.

In 1955 Chambers left Detroit on the road with tenor saxophonist Paul "Vice Pres" Quinichette, then settled in New York, where he worked in quick succession with the two-trombone group of J.J. Johnson and Kai Winding, with Bennie Green's combo, and with pianist George Wallington's quintet at the Café Bohemia in Greenwich Village, a band that also held Jackie McLean, Donald Byrd, and Art Taylor. McLean pointed Miles Davis toward him, and in the fall of 1955, at twenty, Chambers took the bass chair in the quintet Davis was assembling with John Coltrane, Red Garland, and Philly Joe Jones. DownBeat gave him its New Star Award in 1956. The two marathon Prestige sessions of May 11 and October 26, 1956 produced Cookin', Relaxin', Workin', and Steamin'; the Columbia contract produced 'Round About Midnight, Milestones, and, on March 2 and April 22, 1959, Kind of Blue. Chambers also anchored the three orchestral collaborations with Gil Evans, Miles Ahead, Porgy and Bess, and Sketches of Spain. He stayed eight years, the longest continuous tenure of any musician in Davis's 1950s and early-1960s groups.

His own leader catalog runs to seven albums, all of them made inside that same eight-year window. Chambers' Music: A Jazz Delegation from the East came first, cut in Los Angeles on March 1 or 2, 1956 for the small Jazz West label with Coltrane, Kenny Drew, and Philly Joe Jones, and carrying the first Coltrane composition ever committed to record, "John Paul Jones." Blue Note then took him on for three: Whims of Chambers (September 21, 1956), a sextet with Coltrane, Donald Byrd, Kenny Burrell, and Horace Silver; Paul Chambers Quintet (May 19, 1957) with Byrd, Clifford Jordan, Tommy Flanagan, and Elvin Jones; and Bass on Top (July 14, 1957), a pianoless-frontline quartet with Burrell, Hank Jones, and Art Taylor that put the bass in the lead voice for the whole record. Two Vee-Jay dates followed, Go... (February 2 and 3, 1959, Chicago) with Freddie Hubbard and Cannonball Adderley sharing a front line for what was probably the only time in either man's career, and 1st Bassman (May 12, 1960), whose material was written entirely by Yusef Lateef and whose band included Tommy Turrentine and Curtis Fuller. The co-billed trio album We Three, recorded November 14, 1958 with Roy Haynes and Phineas Newborn Jr., rounds out the leader shelf.

Between 1956 and 1962 he was the most heavily booked bassist in New York, and the sideman list reads like a syllabus for hard bop. He is on Coltrane's Blue Train (September 15, 1957) and Giant Steps, whose blues "Mr. P.C." is named for him; on Thelonious Monk's Brilliant Corners, where he replaced Pettiford for the December 7, 1956 session that produced "Bemsha Swing"; on Sonny Rollins's Tenor Madness, which contains Rollins's tribute tune "Paul's Pal"; on Sonny Clark's Cool Struttin', Hank Mobley's Soul Station, Lee Morgan's The Cooker, Art Pepper Meets the Rhythm Section, and Oliver Nelson's The Blues and the Abstract Truth. The Detroit network kept reappearing: he cut Jazzmen: Detroit for Savoy on April 30 and May 9, 1956 with Pepper Adams, Kenny Burrell, Tommy Flanagan, and Kenny Clarke, joined Thad Jones's Motor City Scene in 1959, and played on the Adams/Byrd Bethlehem album that took the same title. He also recorded with Gene Ammons, Milt Jackson, Chet Baker, and Quincy Jones, and appeared on Adams's 1963 Motown-financed leader date Pepper Adams Plays the Compositions of Charlie Mingus.

Chambers and pianist Wynton Kelly left Davis in 1963, and drummer Jimmy Cobb followed them out; the three continued as the Wynton Kelly Trio, one of the most tightly drilled rhythm sections of the decade. They backed Wes Montgomery on Full House in 1962 and again on the live Smokin' at the Half Note in 1965, and in July 1964 Chambers and Cobb flew to Tokyo for the World Jazz Festival in a package under J.J. Johnson's leadership, staying on to record Jazz in Japan with Toshiko Akiyoshi's big band. He played on Herbie Hancock's Inventions and Dimensions on August 30, 1963. One of his last studio dates was Barry Harris's Bull's Eye!, recorded in New York on June 4, 1968 with Pepper Adams, Charles McPherson, Kenny Dorham, and Billy Higgins. By then a heroin habit had given way to heavy drinking, and colleagues' accounts from the mid-1960s describe missed calls and late arrivals. Hospitalized in New York late in 1968 for what was first taken to be influenza, he was found to have tuberculosis, slipped into a coma, and passed away on January 4, 1969 at the age of 33. He was buried after a funeral in Harlem. The tributes had started while he was still alive and kept coming: Coltrane's "Mr. P.C.," Rollins's "Paul's Pal," Red Garland's "The P.C. Blues," Tommy Flanagan's "Big Paul," and Max Roach's "Five for Paul."

Chambers combined a large, centered pizzicato tone with a rhythmic conception that made a walking line feel like forward motion rather than timekeeping, decorating quarter notes with triplet turns and choosing passing tones well away from the obvious root, a habit Ron Carter later extended and Pat Metheny summarized by calling him the all-time champion of groove and note choice. His conservatory training under a Detroit Symphony principal gave him something almost no bebop bassist had: a usable bow. Where Slam Stewart had made arco a novelty, Chambers improvised full choruses with it at tempo, on "Yesterdays" from Bass on Top, across his own Blue Note dates, and most famously in the brief bowed exchange with Bill Evans that opens "So What" on Kind of Blue. He was equally at home under Miles Davis's modal experiments, inside John Coltrane's dense harmonic cycles on Giant Steps, and in the blues-rooted organ-and-tenor settings of the Prestige and Blue Note catalogs, which is why he was booked constantly rather than exclusively. Christian McBride, Ben Williams, and Linda May Han Oh all cite him directly, and Charlie Haden named him the first bassist whose sound he could identify. Discogs lists him on 1,948 credited releases, only 79 of them under a leader or co-leader billing, a ratio that states his career plainly.