The porous ZnO/C composites derived from metal organic framework-5 (MOF-5) is obtained via a calcination method subsequent to hydrothermal process. The results of materials characterization analysis show that the porous ZnO/C composites is well-crystallized with cube morphology and possesses a large specific surface area. According to the electrochemical measurements, the porous ZnO/C composites as anodic materials for Nickel–Zinc rechargeable battery exhibits excellent electrochemical performance compared with that of the commercial ZnO, keeping the discharge specific capacity at 587 mAh g−1 with the capacity retention ratio of about 89.1% after 800 cycles. The outstanding electrochemical property of porous ZnO/C composites can be ascribed to the interconnected conductive network generated by the carbon layer and stable cube architectures derived from metal organic framework-5 precursor, which can facilitate the transportation of electrons and restrain the formation of zinc dendrites during repeated charge-discharge cycling. Furthermore, a novel sphere structure consisting of numerous intersecting disk-like sheets is transformed from the cubic porous ZnO/C composites after 600 cycles, which can contribute to the uniform current distribution and improve the performance of energy storage, revealing the truth for the long cycle life of porous ZnO/C composites.