Photocatalytic deoxygenative carboimination of unstrained γ,δ-unsaturated oximes with π-acceptors including trifluoromethyl alkenes, 1-trifluoromethyl-1,3-butadienes, gem-difluoroalkenes, acrylates, and styrenes has been achieved which provides an efficient and mild approach to construct structurally diverse and highly functionalized pyrrolines with good functional group tolerance. Importantly, upon utilization of trifluoromethyl alkenes as the coupling partners, the developed protocol not only allows the introduction of the extremely valuable gem-difluoroalkene functionality and pyrroline moiety into one molecule, but could also further transform the resulting gem-difluoroalkene-functionalized pyrrolines to the architecturally intriguing indolizine alkaloids via oxidation/reduction and sequential C−F bond cleavage. The mechanistic studies indicated that a free-radical and anionic process was probably involved in this photocatalytic deoxygenative transformation. (Figure presented.). © 2021 Wiley-VCH GmbH