Abstract The gem ‐difluoroalkene moiety has attracted considerable attention from the synthetic chemistry community due to its outstanding performance in the drug design and development. By employing 4‐CzIPN as photocatalyst, a metal‐free synthetic method for gem ‐difluoroalkenes is developed under blue LED irradiation. A wide range of tertiary amines and α‐trifluoromethyl alkenes are applicable in the present gem ‐difluoroallylation and successfully transformed into the gem ‐difluoroalkenes in good yields.