Abstract The polarography of several aliphatic polyamine complexes of Pb(II), Zn(II), and Ni(II), and the anodic stripping polarography of polyamine complexes of Zn(II), Cd(II), Pb(II), and Cu(II) were studied. The aliphatic polyamines used were ethylenediamine(en), 1,3-propanediamine(1,3-pn), 1,2-propanediamine(1,2-pn), diethylenetriamine(den), and triethylenetetramine(trien). These lead(II) complexes gave a one-step reversible wave which was diffusion-controlled. The relation between the logarithm of the concentration of polyamine and the halfwave potential of the Pb(II) complex was straight, so that one species of complex ion was found to be predominant in the bulk of solution. The ionic species in the bulk of solution were found to be Pb(en)22+, Pb(1,3-pn)22+, Pb(1,2-pn)22+, Pb(den)22+, and Pb(trien)2+. The stability constants of these complexes were calculated and were found to increase in the order of Pb(1,3-pn)22+<Pb(en)22+<Pb(1,2-pn)22+<Pb(den)22+<Pb(trien)2+. The polarographic waves of Zn(II)-polyamine and Ni(II)-polyamine complexes were irreversible and diffusion-controlled, so the electrode reactions of these complexes were assumed using Matsuda-Ayabe’s theory. All these polyamine complexes of Zn(II), Cd(II), Pb(II), and Cu(II) gave well-defined anodic stripping polarograms. 1,3-pn was the best complexing reagent among these polyamines, because it gave the best separation of the peaks of the anodic stripping polarograms of the four metal ions. Calibration curves were obtained from 0.01 to 0.10 ppm for Zn(II), Pb(II), and Cu(II), and from 0.001 to 0.010 ppm for Cd(II) in 0.4 M 1,3-pn and 0.2 M KCl media. The effects of acid and base on the anodic stripping polarograms were also studied.