A series of lipophilic liyands, 1-3. featuring an 1,2-ethylendiamino moiety as chelating subunit, one (1, 3) or two (2) chin1 carbons, and an hydroxy function (except for 3) in the proximity of the coordination center, have been synthesized. Their Cu(I1) complexes have been investigated as catalysts for the cleavage of p-nitrophenyl esters of phenylalanine (PhePNP) and phenylglycine (PhgPNP) in the presence of cationic aggregates formed by cetyltrimethylammonimn bromide (CTABr) or ditetradecyldibutylanonium bromide (DMDBAB). Large rate accelerations (up to two order of magnitude) and quite remarkable enantioselectivities (from 11 to 35, as the ratios of the rate constants measured for the faster and slower reacting enantiomers) have been observed. In the case of ligands 1 the S-&and complex reacts faster with the S-substrate and the enantioselectivity increases with the lipophilicity of the substituent of the cbiral carbons. Using ligands 2, having two chiral centers, the mosl favoured situation is reached when all the chiral carbons of ligands and substrate have the same absolute configuration: in such a case, and using DMDBAB as cosurfactant, enantioselectivities as high as 35 have been observed. The result\ are explained on the basis of a different reaction mechanism due to the compartmentalization of tbe reacting species (a ternary complex ligand/Cu(II)/substrate) in different loci of the aggregate. It is suggested that, depending on the hydrophobicity of the ternary complex, the cffcctive nucleophile may switch from the Cu(II)-bound @and's hydroxyl to a Cu(II) bound water molecule. The first mechanism is faster and prevails for the more lipophilic ternary complex.