The stability constants of binary complexes of 2,4-dichlorophenoxyacetic acid (2,4-D), (4-chloro-2-methylphenoxy)acetic acid (2,4-MCPA) and (4-chloro-2-methylphenoxy) propionic acid (2,4-MCPP) with Hg(II), Pb(II) have been calculated at 298 K and at ionic strength m ¼ 0.1 (NaNO 3 ). Potentiometric measurements display two hydroxide complexes for Hg(II): HgH À1 A and HgH À2 A 2 whereas for Pb(II) we observe the formation of three species PbH À1 A, PbH À1 A 2 and PbH À2 A 2 . With regard to the successive complexes, no other system represents this type of complexes under our experimental conditions. The order of capacity of complexation compared to metal for the three ligands is Hg(II)4Pb(II). Finally, the study in solution has been completed by a quantum examination of the structures of the complex of Hg(II) by the AM1 method.