The harmless disposal of lead paste in the spent lead-acid batteries (LABs) remains an enormous challenge in traditional pyrometallurgical recycling. Here, we introduced a hydrometallurgical method for the recycling of the spent LABs’ waste to obtain the β-PbO as a novel zinc ion batteries (ZIBs) active material. The obtained β-PbO exhibits ultra-flat charge/discharge voltage platforms (0.21 mV/(mAh g−1)) and stable specific capacity. During the charge/discharge, the β-PbO spontaneously triggers the formation of (ZnSO4)[Zn(OH)2]3·5H2O (ZHS) micro-sheets as a surface passivation layer. Moreover, the ex-situ X-ray spectra reveal that the reversible phase transformation occurs between PbSO4 and Pb with the assistance of ZHS by adjusting the PH value on the electrode-electrolyte interface. The synergistic two-phase-reaction mechanism generates ultra-flat voltage platforms upon the charge/discharge. This “energy-saving and environment-friendly” recycling route eliminates the major source of emission of pollution particulates/gases compared to the traditional pyrometallurgical recycling, while at the same time replacing energy-consuming and environmentally detrimental processes of synthesis of current ZIBs cathodes.