Neopentyl arenesulfonate react with secondary alkylmagnesium chloride in the presence of Ni(0) catalyst to produce arene compounds via the reductive cleavage of carbon-sulfur bond. Highest yield is obtained by using three equivalents of Grignard reagent to the mixture of arenesulfonate and dppfNiCl2 in Et2O at room temperature. This reaction represents a novel method allowing the efficient hydrogenolysis of sulfur-containing aromatic compounds.