Phosphinated linear polystyrene was synthesized and used as a ligand of palladium catalysts. It showed high activity for the ethoxycarbonylation of 4,4’-dibromobiphenyl (I) in the presence of triethylamine. The catalysts acted as homogeneous under the reaction conditions (150-degrees-C, p(CO) = 10 kg/cm2), and precipitated as solid materials after the reaction. Catalytic performances highly depended on the compositions of the solvent, and the highest activity was achieved in ethanol.