Sulfur-containing organic molecules are recognizedas promising candidates for catalytic C–H functionalization and medicinal chemistry owing to the exceptional ability of the sulfur atom to bind to transition metals and target enzymes. In this study, we report the Rh(III)-catalyzed thione-directed C–H amidation of various thiochromone analogues derived from flavones, isoflavones,and xanthones. Post-transformations of C5-amidated thiochromone products were investigated, and a series of mechanistic studies were performed.