Fluorinated molecules are of paramount importance because of their unique properties. As a result, the search for innovative approaches to the synthesis of this class of compounds has been relentless over the years. Among these, the combination of photocatalysis and organofluorine chemistry turned out to be an effective partnership to access unattainable fluorinated molecules. This Perspective provides an overview of the recent advances in synthesizing fluorinated molecules via an organophotoredox-catalyzed defluorination process from trifluoromethylated compounds. It encompasses the preparation of difluoromethylated (hetero)arenes, amides, and esters as well as