Carbon-sulfur bond formation represents a key step in the synthesis of thioethers, which are a common structural motif in many pharmaceutically compounds. The direct cross-dehydrogenative coupling of C-H/S-H bonds has become a powerful tool for C-S bond formation. As these coupling reactions avoid pre-functionalization of the starting materials, they are more atom-economical, practical, and environmentally friendly than traditional cross-coupling reactions. In this review, we will highlight the most important developments in this novel and interesting research arena with the emphasis on the mechanistic aspects of the reactions. The review is divided into three major sections: (1) C(sp3)-H/S-H bonds coupling reactions; (2) C(sp2)-H/S-H bonds coupling reactions; and (3) C(sp)-H/S-H bonds coupling reactions.