Although different kinds of metal oxide nanoparticles are extensively investigated as anode materials for lithium-ion batteries (LIBs), their cycle life and energy/power density are still not suitable for commercial applications. Metal oxides have a large storage capacity, but they suffer from low electrical conductivity and severe volume change during the charge/discharge process. Herein, we present a facile route to prepare self-assembled ZnO/Co3O4 nanocomposite clusters through calcination of preformed Prussian Blue Analogue (PBA) Zn3[Co(CN)6]2 nanospheres. These self-assembled ZnO/Co3O4 nanocomposite clusters exhibit superior lithium storage capabilities with good cycling properties. A reversible capacity of 957 mA h g(-1) was retained at a current density of 100 mA g(-1) up to 100 cycles. The enhanced electrochemical performance of the ZnO/Co3O4 nanocomposite anode can be ascribed to the rational design of the self-assembled cluster structures and the synergetic effect of two-component functional nanoparticle systems.