Biphenyl derivatives are known to show interesting biological activities, and they have been used to prepare natural products, pharmaceuticals, and homogeneous catalyst ligands. We recently found that the aryl sp(2) C-S bonds in alkyl arenesulfonates were cleaved by the Ni(0) catalyst and the resulting adducts reacted with arylmagnesium bromides to produce the correponding biphenyl compounds. Various biphenyls were prepared by the new C-C cross-couplings of neopentyl arenesulfonates with aryl Grignard reagents in the presence of (dppf)NiCl2 as a catalyst.