We herein present an example of photoinduced catalyst- and metal-free allylic defluorinative alkylation of trifluoromethyl alkenes with Katritzky salts in the presence of an easily available Hantzsch ester or Et₃N. This simple method can accommodate primary alkylamines with primary and secondary carbon, delivering gem-difluoroalkenes with complex and diverse structures. In addition to the sustainable feature of being catalyst- and metal-free, the transformations also show great functional group tolerance and viable functionalization of late-stage biologically and pharmaceutically relevant molecules.