Three artificial mixtures of PbSO4 and PbO2 as well as the active materials obtained directly from the positive plates of spent batteries have been solvothermally treated in methanol at 140 °C for 24 h, which produce mainly PbO·PbSO4. The PbO·PbSO4 can be easily desulphated with ammonium carbonate to produce PbCO3, which can be calcined to form α-PbO to be used as positive active material of lead acid batteries. The α-PbO powders are irregular particles and highly electrochemically active, which discharges around 165 mAh g−1 at 5 mA g−1, 80 mAh g−1 at 200 mA g−1 and 60 mAh g−1 at 400 mA g−1 with excellent cyclic stability in 50 cycles. SEM investigations show that the as-formed PbO·PbSO4 may inherit and enhance the morphological characteristics of PbSO4, and carbonation of PbO·PbSO4 does not destroy the rod-like characteristics. For the active material from the positive plates of spent lead acid batteries, the discharge capacities are 170 mAh g−1 at the current density of 5 mA g−1, and 60 mAh g−1 at 400 mA g−1, which is also similar. In 50 cycles, its capacity loss is only 5%.