Abstract: An obvious solvent effect of the coupling reaction involving 4-methylbenzenesulfonohydrazide was observed by optimization of the reaction conditions. 1,2-Di-p-tolyldisulfane was efficiently obtained via reducting self-coupilng when 4-methylbenzenesulfonohydrazide was heated in solvent of N,N-dimethylformamide; S-(p-tolyl) 4-methylbenzenesulfonothioate was selectively generated whereas 4-methylbenzenesulfonohydrazide was heated in solvent of ethyl acetate. A cross-coupling product of 1-(cyclohexylsulfonyl)-4-methylbenzene was obtained via a free-radical process under the catalysis of cupric acetate monohydrate/di-t-butyl peroxide system when the solvent of cyclohexane was added to 4-methylbenzenesulfonohydrazide. The reaction described here enables a novel, efficient and green synthetic method for S-containing compound construction.