A reductive cross-coupling of gem-difluoroalkenes with diverse unactivated and heteroatom substituted olefins through a Fe-catalyzed hydrogen atom transfer (HAT) strategy is reported. Different from the previous HAT-type olefin cross-coupling reactions, the presence of a fluorine atom in the molecule results in a stereoselective β-F cleavage, leading to a C(sp2)-C(sp3) bond formation. A wide variety of alkylated monofluoroalkenes were obtained in good efficiency with excellent Z selectivity under air- and water-tolerant reaction conditions. A similar defluorinative coupling reaction of monofluoroalkenes was also realized.