Herein, we report a facile, efficient, and practical protocol that enables the preparation of aryl xanthates and aryl dithiocarbamates from functionalized dibenzothiophenium salts via a photoactivated electron donor-acceptor complex. This mild, metal-free method is operationally simple and has a broad substrate scope and potential utility for late-stage functionalization of natural products and pharmaceuticals. Finally, this method also has redefined the substrate scope and reaction pathway for the Leuckart thiophenol reaction.