We commenced this study by probing the feasibility of the gem-difluoroallylation reaction of cyclohexane 1a with α-trifluoromethyl styrene 2a. After optimization of the reaction conditions, a protocol consisting of TBADT (10 mol%), CrCl3 (5 mol%), and K3PO4 (1.2 equiv) under irradiation of violet lightemitting diode (LED) in MeCN furnished the best results, and the desired product 3aa was achieved in 73% isolated yield (Entry 1, Table ). Several diaryl ketone-derived photocatalysts PCs 1-4 were tested, leading to trace product generation (Entry 2). A deleterious effect was observed when replacing CrCl3 with CrCl2 as the co-catalyst (Entry 3). It was notable that K3PO4 was found to be the best base, and all other base sources all resulted in significantly reduced yields (Entries 4-12). Solvent exhibited a pivotal effect on the reactivity, as much lower yields or even shut-down of this reaction were attained with other solvent sources, such as acetone, DMSO, DMF, DMA, toluene, DCM, DME, MTBE, and THF (Entries 13-15). Reducing the loadings of TBADT and CrCl3 resulted in diminished reaction efficiencies. As expected, control experiments demonstrated that TBADT, CrCl3, K3PO4, and light were essential to the occurrence of this reaction (Entries 18-21).