The complexation of Cd
2+, Zn
2+, and both together withthe phytochelatin (
-Glu-Cys)
3Gly is studied by differentialpulse polarography, and data are analyzed by multivariatecurve resolution by alternating least squares (MCR-ALS). MCR-ALS yields the respective unitary voltammograms andconcentration profiles of the resolved components, whichcontain information on the relative stabilities andstoichiometries of the formed complexes. The analysis ofthese results shows, for the Cd
2+/(
-Glu-Cys)
3Gly system, thepresence of different kinds of bound Cd
2+. For the Zn
2+/(
-Glu-Cys)
3Gly system, the poor definition of the reductionsignals of the complexes prevents a clear discriminationamong differently bound Zn
2+ ions. A tentative complexation/electrochemical model is proposed for when both metalions, Cd
2+ and Zn
2+, compete toward complexation, andsome of the corresponding equilibrium constants areestimated.