Quantitative analysis of the complex problem of coupled electron- and proton-transfer steps during reduction of the polyoxo anions α- [P2W18O62]6- and α-[H2W12O40]6- in aqueous NaCl (0.5 M) has been achieved by simulation of cyclic voltammograms (Rudolph, M.; Reddy, D. P.; Feldberg, S. W. Anal. Chem. 1994, 66, 589A) over wide ranges of anion concentration, pH, and scan rate. Since there are too many unknown parameters to attempt a one-step global form of simulation, a systematic, stepwise approach has been adopted by progressively accessing regimes of increasing voltammetric complexity. This protocol allows experimental behavior in each system over 5 orders of magnitude in proton concentration to be simulated by estimation of three protonation constants combined with experimentally determined reversible half-wave potentials for the two one-electron processes involved. Fast electron transfer and protonation kinetics are assumed. The importance of the values chosen for the diffusion coefficients of the proton and polyoxo anion species is considered. The simulations account for the fact that pairs of one-electron processes coalesce to give an apparent two- electron process in the pH range 1-6 for reduction of both anions.