Terphenyls and biphenyls, which are frequently found in natural products and pharmaceuticals, are famous for their biological and optical activities. We synthesized various asymmetric terphenyl derivatives in high yields by the palladium-catalyzed reaction of neopentyl 4-bromobenzenesulfonate with arylboronic acids followed by the nickel-catalyzed coupling with arylmagnesium bromides. Arenesulfonates proceeded the reaction in the presence of a nickel(0) catalyst via an overall nucleophilic aromatic substitution of the alkyloxysulfonyl group in reactions with Grignard reagents, while they did not react with a palladium catalyst at all. This reaction demonstrates that bromoarenesulfonates are plausible presursors for the preparation of asymmetric oligophenyls and other conjugated compounds.