Photoinduced ligand-to-metal charge transfer (LMCT) is a powerful technique for the formation of reactive radical species via homolytic cleavage of the metal–ligand bond. Here, we present that the excited state LMCT of a cobyrinate complex can be accessed by tuning its axial coordination with thiolates as ligands. We demonstrate the photoreduction of cobalt via the excited state Co–S bond homolytic cleavage, as guided by the DFT calculations, which signify the relevance of thiolate axial ligands facilitating the LMCT reactivity. By exploiting this excited state LMCT of cobyrinate, we developed a catalyst-controlled activator regeneration mechanism to catalyze an efficient atom transfer radical polymerization (ATRP) under low-energy light irradiation. Tuning the coordination sphere of cobyrinate provides further control over the electronic properties of the complex while also accessing photothermal conversion in mediating ATRP catalysis.