A highly regioselective C–H/S–H cross-coupling of imidazo[1,2-a]pyridines with thiols has been developed using molecular oxygen to form the C-3 sulfenated products in the presence of a copper catalyst. It represents a simple process for the formation of C–S bonds to prepare thioether-decorated imidazo[1,2-a]pyridines. The reaction proceeds smoothly with a broad range of substrates to give imidazo[1,2-a]pyridines in good yields.