A native of Atlanta, Jones was a graduate of Henry McNeal Turner High School. After playing baseball for an Atlanta semi-pro team, Jones was signed by the Milwaukee Braves as an amateur agent in 1958. In his major-league debut, on July 13, 1961, Jones tied a "modern" (post-1900) National League record by collecting four hits (three singles and a double) in his first game, a 6-4 Braves road win over the St. Louis Cardinals and future Baseball Hall of Famer Bob Gibson. Leading off the game, Jones' first career hit was a single off Gibson. An inning later he notched his first career run batted in with a double off Gibson that scored Joe Torre.
Jones' most productive season came in 1965, when he batted .262 with 31 home runs and 75 runs batted in. Jones teamed up that year with Hank Aaron, Eddie Mathews, Joe Torre, Felipe Alou, and Gene Oliver, as the Braves set a National League record with six 20-home run hitters in one season. When the Braves moved to Jones' native Atlanta in 1966, he hit 23 homers despite a shoulder injury. In 1967, he was traded to Cincinnati.
In the 1968 MLB expansion draft, Jones was the second player selected by the Montreal Expos (the fourth pick overall), behind Manny Mota.
On April 8, 1969 at Shea Stadium in Flushing, New York, playing the Mets, history was made. Jones, along with Don Hahn and Rusty Staub, took the outfield in the bottom of the first inning for the first-day Expos. The trio made up the Expos' first outfield in Montreal franchise history with Jones in left field for the Expos.
Six days later, on April 14, 1969, Jones hit a three-run home run and two-run triple in the Expos' first home victory as a franchise, an 8-7 win over the St. Louis Cardinals at Jarry Park. The home run came with Staub and Don Bosch on base and was the very first to be hit in a Major League regular season game in Canada. Jones finished that season with a career-high .270 batting average, 22 homers and 79 runs batted in. So popular was Jones in Montreal that the left-field bleachers in Jarry Park were nicknamed "Jonesville."
In an 11-year career, Jones was a .252 hitter with 133 home runs, 415 RBI, 485 runs, 132 doubles, 31 triples, and 65 stolen bases in 1002 games.
A former Triple-A Syracuse Chiefs outfielder, Jones had one of the best seasons ever by a Syracuse baseball player in 1964, when he batted .317 with 15 doubles, 18 triples, 39 home runs and 102 runs batted in. He holds modern-day single-season Syracuse records for runs (111), total bases (337), RBIs, triples and home runs, all set in 1964. Jones was part of a famed Syracuse Chiefs outfield that season that included future major-league stars Willie Horton and Jim Northrup.
Jones was inducted into the Syracuse Baseball Wall of Fame in 2000, and into the International League Hall of Fame in 2013.
Mack Jones died in Atlanta of complications from stomach cancer at age 65. He was survived by his wife Esther Levon Buggs Hill Jones, daughter Gayle Jones, son Rontae Jones, three grandchildren and stepson Antonio Hill.
Jones is portrayed by actor Phillip Jarrett in the French-Canadian baseball film A No-Hit No-Run Summer.