Light-driven carbon dioxide (CO 2 ) capture and utilization is one of the most fundamental reactions in Nature. Herein, we report the first visible-light-driven photocatalyst-free hydrocarboxylation of alkenes with CO 2 . Diverse acrylates and styrenes, including challenging tri-and tetrasubstituted ones, undergo anti-Markovnikov hydrocarboxylation with high selectivities to generate valuable succinic acid derivatives and 3-arylpropionic acids. In addition to the use of stoichiometric aryl thiols, the thiol catalysis is also developed, representing the first visible-lightdriven organocatalytic hydrocarboxylation of alkenes with CO 2 . The UV-vis measurements, NMR analyses, and computational investigations support the formation of a novel charge-transfer complex (CTC) between thiolate and acrylate/styrene. Further mechanistic studies and density functional theory (DFT) calculations indicate that both alkene and CO 2 radical anions might be generated, illustrating the unusual selectivities and providing a novel strategy for CO 2 utilization.