Abstract An efficient method for the construction of fluorinated benzo[a]quinolizidines from α‐trifluoromethyl alkenes and dihydroisoquinoline acetic acids using visible light photocatalysis was developed. The reaction was accomplished through a decarboxylative/defluorinative cross‐coupling, followed by an intramolecular defluorinative C−H functionalization in one‐pot. Diversified fluorinated benzo[a]quinolizidines, which are less accessible by other methods, were obtained in good yields with high diastereoselectivity. magnified image