Admitted to the bar, he successively practiced in Westfield, Monson, and Ware, before settling in Springfield, Mass., where he practiced in partnership with Whig politician George Ashmun as Chapman & Ashmun.
He was a presidential elector for Lincoln in 1860, and served on the Harvard Board of Overseers.
He handled some legal matters for John Brown when Brown was in business in Springfield, and later, when Brown was imprisoned in Virginia facing hanging after the abortive Harper's Ferry raid, he wrote to Chapman asking him to either come himself or send legal assistance: "I have money in hand here to the amount of $250 [...] do not send an ultra abolitionist," which Chapman was unable to do at the time.
[2][3] His younger sister was Clarissa Chapman Armstrong, a missionary teacher in the Hawaiian Islands.
Through her, Reuben Atwater Chapman was uncle to Samuel Chapman Armstrong, an American Civil War general and founder of Hampton Institute, and to William Nevins Armstrong, Attorney General in the Kingdom of Hawaii.