Hybrid materials based on PbO 2 and PANi were prepared by cyclic voltammetry combined with chemical method. Firstly, PbO 2 and PbO 2 -PANi were deposited on stainless steel by cyclic voltammetry (CV) at a scan rate of 100 mV s −1 . Next, they were immersed in acidic aniline solution (0.1 M) to form new fresh PbO 2 -PANi composites. The properties of materials were characterized by x-ray diffraction, IR-spectroscopy, scanning electron microscopy and transmission electron microscopy. The electrocatalytic oxidation for methanol of all PbO 2 -PANi layers was investigated in acidic medium by potentiodynamic measure at a scan rate of 100 mV s −1 in the range of 1.4 V to 2.2 V versus Ag/AgCl/saturated KCl electrode. The obtained results indicated that the composites prepared by above combined method could significantly enhance the electrocatalysis for oxidation of methanol.