The cleavage of sulfidic C-S bonds under visible-light irradiation was harnessed to generate carbocations under neutral conditions and synthesize valuable di- and triarylalkanes as well as benzyl amines. To this end, photoredox catalysis and direct photoinduced C-S bond cleavage are used as complementary approaches and participate in the versatility of the general strategy. Extensive mechanistic studies have demonstrated the diversity of the reaction mechanism at work in these different reactions.