Green reached the majors in 1898 with the Chicago Orphans (later the Cubs), spending four years with them before moving to the Chicago White Sox. Green became the regular Orphans center fielder in 1898, replacing the moody Bill Lange, who retired at the height of his fame to get married. Green hit .304 for the Orphans during four seasons, including a career-high .313 in 1901. But when the American League owners started to offer lucrative contracts to unsatisfied National League stars, Charles Comiskey landed Green, who became the White Sox right fielder in 1902. In his first two years with the Sox he hit .312 and .309. A fast and smart runner, from 1900 to 1904 he averaged 30.2 stolen bases in each season, with a career-high 35 in 1902. Then, before the 1906 season he suffered a throwing arm injury and was outrighted to the American Association.
Green died in Camden, New Jersey just three days after his 38th birthday. While Green's family always insisted he died of complications from a beaning, the book, Death At the Ballpark reveals Green most likely died from complications of syphilis.