A novel and facile synthetic approach is developed to prepare the PbO@C nanocomposites by using starch as the carbon precursors. Nearly monodispersive lead oxide nanoparticles embedded carbon nanocomposites are produced via pyrolyzing Pb(NO3)2 impregnated starch gel under the N2 atmosphere at 700 °C. The PbO nanoparticles are ca. 10 nm in size and slightly changed with the [Pb(NO3)2:starch] ratios varied. XRD patterns and XPS data reveal the presence of α-PbO, orthorhombic β-PbO and Pb in the nanocomposites without any tetravalent Pb4+ species. When used as anode materials for the lead-acid battery, the nanocomposites exhibit an improved performance. PbO@C nanocomposites prepared from the mixtures with [Pb(NO3)2:starch] of 70:30, 50:50 and 30:70 exhibited the highest capacity of 205 mA h g−1, the highest residual capacity of 185 mA h g−1 and the best cyclic stability after 100 charge/discharge cycles, respectively.