In order to explore how to improve the electrochemical performance of the lead-acid battery positive active material, PbO2 particles with multiple morphologies and phases including urchin-like and ball-like β-PbO2 particles with size of 0.5–1 μm, flower-like α-PbO2 particles with size of 1–2 μm are chemically synthesized. These samples are composed of different smaller nanoparticles. The electrode made with urchin-like β-PbO2 and flower-like α-PbO2 in the ratio of 1:1 can deliver a discharge capacity of 183 mA h g−1 at 0.1 C after 100 cycles, and subsequent rate performance test shows that a discharge capacity of 97.2 mA h g−1 can be obtained even at 1 C. Moreover, this kind of electrode pretreated in 1 M H2SO4 solution displays improved stability of cycle, a capacity of 146.7 mA h g−1 can be obtained after 100 cycles, and its corresponding active material utilization ratio can reach 65%.