The aim of this paper is to propound a novel conception of a comparison electrode, allowing the evaluation of both anode and cathode polarizations involved in the all-solid Zn/PbO2 cell. This consists of separating each electrode layer deposited on the electrolyte pellet into two distinct parts. During discharge, one of these parts, which will be crossed by the current, acts as a working electrode while the other, staying at its equilibrium state, can play the role of a comparison electrode. First, the reversibility and the potential stability of the comparison electrode are checked. Subsequently, the method is applied to demonstrate the effect of electrode morphology and current density of discharge on electrode polarization in the Zn/PbO2 system.