Looking for electrodes with a high overpotential for the oxygen evolution reaction (OER), useful for the oxidation of organic pollutants, Ti/PbO2 electrodes were prepared by a thermal-electrochemical method and their performance was compared with that of electrodeposited electrodes. The open-circuit potential for these electrodes in 0.5 mol L-1 H2SO4 presented quite stable similar values. X-ray diffraction analyses showed the thermal-electrochemical oxide to be a mixture of ort-PbO, tetr-PbO and ort-PbO2. On the other hand, the electrodes obtained by electrodeposition were in the tetr-PbO2 form. Analyses by scanning electron microscopy showed that the basic morphology of the thermal-electrochemical PbO2 is determined in the thermal step, being quite distinct from that of the electrodeposited electrodes. Polarization curves in 0.5 mol L-1 H2SO4 showed that in the case of the thermal-electrochemical PbO2 electrodes the OER was shifted to more positive potentials. However, the values of the Tafel slopes, quite high, indicate that passivating films were possibly formed on the Ti substrates, which could eventually explain the somewhat low current values for OER.