Direct manipulation of readily accessible trifluoromethyl alkenes (TAs) represents an attractive approach to the preparation of diversified fluorine‐containing compounds. In this study, defluorinative alkylation reactions of TAs with a broad array of soft carbon nucleophiles have been documented. Nucleophilic substitutions occur enabled by a catalytic amount of base, providing access to tertiary alkyl substituted gem‐difluoroalkenes and 2‐fluoro‐4H‐pyrans. By extending the nucleophiles to silyl enol ethers, defluorination can be achieved in the absence of base to give gem‐difluoroalkenes. This process, which eliminates the requirement of organometallic reagents, transition metals, or strong bases for the C−F bond cleavage, is applicable to late‐stage modification of complex molecules.