Several modifications of manganese dioxide (MnO2) were investigated for use in composite electrode materials for oxygen evolution, the target application being anodes for the industrial electrowinning of metals. It is demonstrated that the performance of this material depends strongly on the modifications of MnO2. All modifications investigated were found to be more active than the usual anode of lead alloyed with silver (PbAg) used in zinc electrowinning. A composite sample containing chemical manganese dioxide (CMD) was found to give an oxygen evolution overpotential 0.25 V lower than the standard PbAg anode material. In the second part of the article, we investigate the effect of varying several parameters of the composite electrode assembly, including the size of the catalyst particles and percentage of the catalyst material used. A model is proposed where the performance of the material is proportional to the total length of the boundaries between the lead matrix material and the MnO2 catalyst particles. Physicochemical processes contributing to the observed data are discussed.