The effects of antimony on the electrocrystallization and on the electrochemical behavior of α and β lead dioxide were investigated by scanning electron microscopy, x‐ray diffraction, and chemical analysis. Galvanostatic reduction tests in alkaline solutions were also performed. Antimony drastically modifies the crystal morphology of α lead dioxide and, up to a concentration of 0.2%, changes the O/Pb ratio by filling lattice vacancies. On
β PbO2
, on the contrary, antimony does not seem to have any significant influence. The reduction tests on lead dioxide showed that the cathodic process occurs in a homogeneous system until the O/Pb ratio reaches a value depending on the dioxide allotropic form and on the antimony content. The O/Pb ratio of intermediate oxide increases from pure
α PbO2
(1.33) to Sb‐doped
β PbO2
(1.65).