A CuI-catalyzed direct access to sulfides from disulfides via C-H bond cleavage of di- or trimethoxybenzene is described. The procedure utilizes O(2) as a clean and cheap oxidant. Direct selenation of the C-H bond also took place under this procedure. Furthermore, the system enables the use of two RS in (RS)(2). Thus, it represents an atom-economical procedure for the synthesis of sulfides and selenides.