The organic chemical hydride method using the toluene (TL)/methylcyclohexane (MCH) system is one of the prospective energy carrier technologies for hydrogen storage and transportation. The direct electrohydrogenation of toluene with water decomposition using electric power is a highly efficient energy conversion process for the MCH synthesis. In this process, an IrO2-based directionally stable electrode® (DSE®) for the oxygen evolution reaction (OER) is used as the anode because of its good electrocatalytic activity and durability. However, further improvement in the activity is needed for practical applications. In this study, the effect of Zr addition substituted for Ta in IrO2-Ta2O5/Ti, which is a typical OER anode, on the electrocatalytic activity has been investigated in sulfuric acid with TL contamination. The activity of both the IrO2-Ta2O5/Ti and the IrO2-Ta2O5-ZrO2/Ti was higher and less affected by TL contamination than the IrO2/Ti. The activity of the IrO2-Ta2O5-ZrO2/Ti increased with the Zr content. The Zr addition increased the real surface area along with the increase in the double layer capacitance; on the other hand, the increase in activity was more than that of the surface area. Therefore, the Zr additive would affect not only the real surface area increase, but also the electrocatalytic activity.