The hydrosoluble complexes [Rh(CO)(Pz)(L)](2,) and [RuH(CO)(CH3CN)(L)(3)][BF4] [L = TPPMS (triphenylphosphinemonosulfonated) and TPPTS (triphenylphosphine-trisulfonated)] were evaluated in the selective hydrogenation of alpha,beta-unsaturated aldhydes in biphasic media The Rh complexes produced the saturated aldehydes while the Ru complexes generated the alcohols with high chemoselectivity. The catalytic phase can be recycled up to five times.