In this work, PbCl2/Sb4O5Cl2 and PbSbO2Cl are prepared by a simple solution route, and compared by using as lithium storage materials. PbCl2/Sb4O5Cl2 is the intermediate precursor for hydrothermal preparing PbSbO2Cl. Morphology analysis shows that PbCl2/Sb4O5Cl2 is composed of irregular particles in the range of 50–100nm and PbSbO2Cl consists of well-dispersed bulks with the particle size of 200–500nm. Similar chemical composition between PbCl2/Sb4O5Cl2 and PbSbO2Cl make they show similar electrochemical behaviors. However, different morphology and structure also make PbCl2/Sb4O5Cl2 and PbSbO2Cl exhibit different lithium storage capacity and cycling performance. Charge/discharge tests reveal that nanocomposite PbCl2/Sb4O5Cl2 can deliver a higher initial lithiation capacity (1036.7mAhg−1) than PbSbO2Cl (993.8mAhg−1). Upon repeated cycles, PbCl2/Sb4O5Cl2 also shows better electrochemical properties than PbSbO2Cl, which may be contributed to the maintaining of structural stability by nanocomposite structure. As a result, PbCl2/Sb4O5Cl2 delivers a reversible capacity of 339.7mAhg−1 after 30 cycles.