The sulfhydryl-directed peri-selective C-H bond activation and tandem cyclization of naphthalene-1-thiols with alkynes proceed efficiently. Most products of naphthothiopyrans with various substituents are achieved in good yields under rhodium catalysis. This protocol has some advantages over the traditional methods in synthesizing naphtho[1,8-bc]thiopyrans in terms of stable coupling substrates, simple operation, peri-selectivity, and atom and step economy.