Synergism in the extraction of Zn(Il) and Cd(II)with chloroform solution of propionic, butyric and valeric acids in the presence of n-butylamine, dibutylamine, tributylamine, β-picoline, pyridine and quinoline is reported The effect of various parameters affecting extractions has been investigated The compositions of synergistic adduct extracted into the organic phase have been proposed on the basis of slope analysis method. In general the species have been represented as MA2.2HA.B (aliphatic amine system and MA2.2HA.2B (heterocyclic amine system), where M = zn(Il)/CdII), HA = acid and B = amine. On the basis of extraction constant (Kex) values the relative effectiveness of different amines as synergists has been compared. Based on the extraction data some separations of metal ions have also been reported with fairly high separation factor (β).