In 1833, Bibb married another mulatto slave, Malinda, who lived in Oldham County, Kentucky. They had a daughter, Mary Frances.
In 1842, he managed to flee to Detroit, from where he hoped to gain the freedom of his wife and daughter. After finding out that Malinda had been sold as a mistress to a white planter, Bibb focused on his career as an abolitionist. He traveled and lectured throughout the United States.
In 1849-50 he published his autobiography Narrative of the Life and Adventures of Henry Bibb, An American Slave, Written by Himself, which became one of the best known slave narratives of the antebellum years. The passage of the Fugitive Slave Act of 1850 increased the danger to Bibb and his second wife Mary E. Miles, of Boston. It required Northerners to cooperate in the capture of escaped slaves. To ensure their safety, the Bibbs migrated to Canada and settled in Sandwich, Upper Canada now Windsor, Ontario.
In 1851, he set up the first black newspaper in Canada, the Voice of the Fugitive. Due to his fame as an author, Bibb was reunited with three of his brothers, who separately had also escaped from slavery to Canada. In 1852 he published their accounts in his newspaper.
He died young, at the age of 39.