Pd-catalyzed cross-coupling of 2-bromo-3,3,3-trifluoropropene (BTP) and arylmagnesium bromides was investigated. Diphenylphosphinomethane (dppm) was exclusively effective in the coupling among the phosphine ligands tested with Pd(0) and Pd(II) complexes. The use of diphenylphosphinomethane-coordinated Pd(II) complex, PdCl2(dppm), resulted in the highest yield of alpha-trifluoromethylstyrene (98%) from 2-bromo-3,3,3-trifluoropropene and phenylmagnesium bromide in 1,4-dioxane solvent at 50 C for 30min. The PdCl2(dppm)-catalyzed coupling could be applied to the synthesis of alpha-trifluoromethylstyrene derivatives with satisfactory yields using arylmagnesium bromides. (C) 2009 Published by Elsevier B.V.