A broadly applicable method for the trifluoromethylthiolation of methylene C(sp3)-H, methine C(sp3)-H, α-oxygen C(sp3)-H, and formyl C(sp2)-H bonds is presented using the decatungstate anion as the sole catalyst. By adjusting the substrate ratio and reaction concentration, this method was applied to 40 examples in good regioselectivities, including the derivatization of natural products. Furthermore, SCF3-drug analogues were synthesized by subsequent functionalization of the SCF3 products, highlighting the importance of this photocatalyzed C-H functionalization.