During one of Bibb's lecture tours, he met Mary Miles of Boston and the couple married in June, 1848.
In January 1851, Bibb joined with Josiah Henson to form the Refugees' Home Colony in Canada for escaped slaves. He also established Canada's first African American newspaper, The voice of Fugitive. One of the newspaper's regular contributions was Martin Delaney. During his period Bibb led the campaign to persuade fugitive slaves and free African Americans to settle in Canada.