AbstractAn electroreductive access to gem‐difluoroalkenes has been developed through the decarboxylative/defluorinative coupling of N‐hydroxyphtalimides esters and α‐trifluoromethyl alkenes. The electrolysis is performed under very simple reaction conditions in an undivided cell using cheap carbon graphite electrodes. This metal‐free transformation features broad scope with good to excellent yields. Tertiary, secondary as well as primary alkyl radicals could be easily introduced. α‐aminoacids L‐aspartic and L‐glutamic acid‐derived redox active esters were good reactive partners furnishing potentially relevant gem‐difluoroalkenes. In addition, it has been demonstrated that our electrosynthetic approach toward the synthesis of gem‐difluoroalkenes could use an easily prepared Kratitsky salt as alkyl radical precursor via a deaminative/defluorinative carbofunctionalization of trifluoromethylstyrene.