Herein, we describe the synthesis of 5-fluoro-dihydroindolizines via dual C-F bond cleavage in a trifluoromethyl group. The photocatalytic defluorinative coupling of pyrrole-2-acetic acids and α-trifluoromethyl alkenes cleaved the first C-F bond, providing gem-difluoroalkenes bearing an unprotected pyrrole motif. Subsequently, an intramolecular SNV reaction closed the ring by forming a C-N bond concomitantly with the cleavage of the second C-F bond. Using indole-2-acetic acids as the substrates, the reactions also allow the assembly of 6-fluoro-dihydropyrido[1,2-a]indoles.