The coupling reaction of pinacolborane with various aryl bromides in the presence of a catalytic amount of Pd(OAc)(2) together with DPEphos as ligand and Et3N as base provided arylboronates. High yields were obtained in the case of electron-donor substituted aryl bromides. The direct preparation of arylboronates allowed the one-pot, two-step synthesis of unsymmetrical biaryls in high yields.