Hybrid materials based on PbO2 and PANi were prepared by cyclic voltanunetry combined with chemical method. Firstly, PbO2 and PbO2-PANi were deposited on stainless steel by cyclic voltammetry (CV) at a scan rate of 100 mV/s. Next, they were immersed in acidic aniline solution (0.1 M) to form new fresh PbO2-P ANi 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 PbO2-PANi layers was investigated in acidic medium by potentiodynamic measure at a scan rate of 100 mV/s 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.