The α-PbO2 deposition layers were prepared on the surface of A1/Pb substrates by constant current electrosynthesis from an alkaline bath, and A1/Pb/α-PbO2 composite inert anode materials were obtained. The effects of the bath composition and bath temperature on the electrosynthesis of α-PbO2 were investigated by means of anodic polarization method, the phase structures and surface microstructures of AI/Pb and α-PbO2 deposition layers were tested by means of X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. The experimental data have shown that the process of α-PbO2 formation have several stages. The appropriate conditions can effectively improve the formation rate of α-PbO2 and avoid the occurrence of oxygen evolution reaction. The α-PbO2 deposition layer obtained in alkaline bath possesses rhombic structure, and it is composed of well developed spherical unit cells.