Voltammetric and coulometric results are described for the electrocatalytic oxidation of Cr(III) to Cr(VI) at the mixed bismuth(V)-lead(IV) dioxide film electrodes (designated Bi-PbO2) that are electrodeposited from acidic solutions of Pb(II) containing Bi(III). A current efficiency of 99.2% (sigma = 1.1%, N = 12) is obtained for galvanostatic generation of Cr(VI) at a preconditioned Bi-PbO2 film electrode. Preconditioning of the Bi-PbO2 film merely involves the generation of Cr(VI) which, based on scanning electron micrographs, is concluded tentatively to achieve chemical stripping of noncatalytic portions of the Bi-PbO2 films to produce films having greater electrocatalytic activity for the desired reaction. Electrochemical stripping of the Bi-PbO2 electrode had a similar preconditioning effect. Based on wavelength dispersive spectroscopy, electrochemical stripping resulted in an increase in surface Bi concentration of 33% relative to Pb.