A variety of alkylarenes were prepared by the coupling reaction of neopentyl arenesulfonates with alkyl Grignard reagents in the presence of a nickel catalyst. Methyl-, n-butyl- and benzylmagnesium halides reacted in good yields of the coupling products, while secondary alkylmagnesium halides underwent the reductive cleavage as well as the coupling reaction. This reaction seems to be useful for the productive and creative cleavage of alkoxysulfonyl groups attached on the aromatic compounds.