After determining the optimal reaction conditions, we then explored the substrate scope of this visible-light-induced synergistic W/Cr catalyzed gem-difluoroallylation reaction of alkanes with α-trifluoromethyl alkenes. First, a diverse set of unactivated alkanes were evaluated. As shown in Scheme 2A, cyclic alkanes with different sizes of rings, such as cyclohexane, cyclopentane, cycloheptane, cyclooxtane, cyclododecane, norbornane, and adamantine, were all proved to be effective coupling partners, thus providing the desired products 3aa-3ga in 43-73% yields. Notably, the gem-difluoroallylation of norbornane site selectively occurred at the bridgehead carbon to forge gem-difluoroalkene 3fa as a single isomer, whereas adamantine preferred to functionalize at the tertiary Csp 3 -H bonds with good regioselectivity. Then, various linear alkanes were investigated and found to be competent substrates. Moderate to good yields were achieved for products 3ha-3la despite with poor regioselectivity. It was found that tertiary Csp 3 -H bonds were preferred compared with secondary Csp 3 -H bonds, and primary Csp 3 -H bonds were least prone to functionalize. Scheme 2. Substrate scope of gem-difluoroallylation reaction of alkanes with α-trifluoromethyl alkenes.