The mild and sustainable methods for C-H direct trifluoromethylation of (hetero)arenes without any base or strong oxidants are in extremely high demand. Here, we report that the photo-generated electron-hole pairs of classical semiconductors (CdS or g-C3N4) under visible light excitation are effective to drive C-H trifluoromethylation of (hetero)arenes with stable and inexpensive CF3SO2Na as the trifluoromethyl (TFM) source via radical pathway. Either CdS or g-C3N4 propagated reaction can efficiently transform CF3SO2Na to radical (CF3)-C-center dot radical and further afford the desired benzotrifluoride derivatives in moderate to good yields. After visible light initiated photocatalytic process, the key elements (such as F, S and C) derived from the starting TFM source of CF3SO2Na exhibited differential chemical forms as compared to those in other oxidative reactions. The photogenerated electron was trapped by chemisorbed O-2 on photocatalysts to form superoxide radical anion (O-2(center dot)) which will further attack radical (CF3)-C-center dot radical with the generation of inorganic product F- and CO2. This resulted in a low utilization efficiency of radical (CF3)-C-center dot (<50%). When nitro aromatic compounds and CF3SO2Na served as the starting materials in inert atmosphere, the photoexcited electrons can be directed to reduce the nitro group to amino group rather than being trapped by O-2. Meanwhile, the photogenerated holes oxidize SO2CF3 into radical (CF3)-C-center dot. Both the photogenerated electrons and holes were engaged in reductive and oxidative paths, respectively. The desired product, trifluoromethylated aniline, was obtained successfully via one-pot free-radical synthesis. (C) 2020 Elsevier Inc. All rights reserved.