The preparation of new palladium complexes that are composed of a series of chiral dipyridylphosphines [(R)-P-Phos (1), (R)-tol-P-Phos (2) and (R)-Xyl-P-Phos) (3)] have been described. The structure of the complex [{(R)-1}Pd(H2O)(2)](OTf)(2) was unambiguously determined by single-crystal X-ray diffractometry. These complexes were found to be effective in the asymmetric bis-methoxycarbonylation of styrene, reaching up to 84% e.e. and 79% chemoselectivity for dimethyl-2-phenylsuccinate (DMPS) under the optimal conditions. In addition, the complexes exhibited almost identical enantioselectivity on DMPS. (C) 2002 Elsevier Science B.V All rights reserved.