Visible‐light‐induced decarboxylative and deboronative radical addition of aliphatic carboxylic acids and arylboronic acid pinacol esters to electron‐deficient alkenes using two‐molecule organic photoredox catalysts, such as dibenzog,pchrysene as an electron donor and 1,4‐dicyanobenzene as an electron acceptor, proceeded efficiently to furnish radical adducts via the generation of alkyl and aryl radicals. The base and substrate play important roles in this photochemical system, and the sequential photoinduced decarboxylation of glutamic acid having two different carboxy groups was successful. Visible‐light‐induced decarboxylative and deboronative radical addition of aliphatic carboxylic acids and arylboronic acid pinacol esters to electron‐deficient alkenes using two‐molecule organic photoredox catalysts, such as dibenzog,pchrysene and 1,4‐dicyanobenzene, proceeded efficiently to furnish radical adducts via the generation of alkyl and aryl radicals.