The influence of ZrO2 particles on fluorine-doped lead dioxide electrodeposition process on the glass carbon electrode (GCE) from lead nitrate electrolytes was studied by cyclic voltammetry (CV) and chronoamperometry (CA), coupled with the scanning electron microscope (SEM). Instantaneous nucleation mechanism is found for fluorine-doped lead dioxide electrodeposition in the presence of ZrO2 particles according to Scharifker–Hills’ model with three-dimensional growth. The results show that the addition of ZrO2 particles decrease the active surface area of the GCE, and the growth of the lead dioxide crystallites was obstructed.