Nanostructural lead oxides were prepared by the decomposition of a new type of lead citrate precursor (Pb-3(C6H5O7)(2)center dot 3H(2)O), which was synthesized through leaching of spent lead acid battery paste in citrate salt aqueous system and more economical compared with former precursor (Pb(C6H6O7)center dot H2O). The products were characterized by thermogravimetric-differential thermal analysis, scanning electron microscopy and X-ray diffraction. The results show that when lead citrate of columnar-shape crystals are calcined in N-2 gas, orthorhombic beta-PbO is the main product containing small amount of Pb and C. On combusting the citrate in air, a mixture of orthorhombic alpha-PbO, tetragonal alpha-PbO and Pb with the particle size of 100-200 nm is obtained, with beta-PbO as the major product. And the cyclic voltammetry measurements of lead oxides present different electrochemical redox potentials because of the different structure of lead oxide obtained from Pb-3(C6H5O7)(2)center dot 3H(2)O. Crown Copyright (C) 2013 Published by Elsevier Ltd. All rights reserved.