A novel nanostructured leady oxides comprising porous carbon skeleton has been synthesized by thermal decomposition of lead citrate precursor, recovered from spent lead-acid battery paste. The influences of O2 percentage in the calcination atmosphere (O2/N2 mixture) and the temperature on leady oxide product characteristics are studied by chemical analysis, scanning electron microscopy (SEM) and X-ray diffraction (XRD). The major crystalline phases of the products are identified as lead oxides, metallic Pb, and carbon. Porous carbon is observed as skeletons within the leady oxide (PbO containing some Pb metal) particles. Mass percentage of Pb metal in the leady oxide increases with increasing the proportion of oxygen in the calcination atmosphere. However, the amount of carbon decreases from approximately 8.0 to 0.3 wt%, and the porous carbon skeleton structure is gradually damaged with oxygen concentration increasing. A model about the thermal decomposition of lead citrate precursor is firstly proposed to elucidate these observations. The nanostructured leady oxides combined with porous carbon can be directly used as precursor of active materials in a new lead acid battery.