An efficient and stereoselective catalytic system has been reported for the Mizoroki-Heck cross coupling using a moderately bulky and electron-rich biphenyl-based phosphine, P(o-C6H4C6H4Me)Ph-2 and a low Pd(OAc)(2) loading. It is found that the nature of olefin has more beneficial effect on the reaction times and yields than the aryl halide which may be due to more contribution of the coordination and/or insertion of the olefin in the rate-determining step of the Heck reaction. (C) 2009 Elsevier B.V. All rights reserved.