Selective direct synthesis of symmetric acetals through a tandem aerobic oxidation-acetalization of primary alcohols, using a chloride-free Pd(OAc)(2)/Cu(OAc)(2)/p-TsOH system as an efficient bifunctional catalyst, has been developed. The reactions occur in neat alcohols with no use of other solvent under mild conditions (50-80 degrees C, 1-10 atm). p-Toluenesulfonic acid exerts a great accelerative and catalyst stabilizing effect, showing a synergism with Cu(OAc)(2). Bimetallic Pd-Cu catalysis is suggested in these reactions. Under similar conditions, a secondary alcohol, propanol-2, reacts more slowly giving mainly acetone. Conventional palladium catalytic systems, such as PdCl2/CuCl2, Pd(OAc)(2)/LiNO3, and Pd(OAc)(2)/Pyridine, showed no or very low activity in the oxidation of neat n-butanol. (c) 2007 Published by Elsevier B.V.