The ZnO/SnO2 composites are synthesized by a simple hydrothermal route and proposed as a novel anodic material for Zn/Ni secondary cells. The structures and morphologies of the samples are characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM). The composite materials are composed of homogeneous grain-like nanoparticles, and a prismatic microstructure is formed between ZnO and SnO2. The electrochemical performances of composite material electrodes are comparatively analyzed through cyclic voltammetry, tafel plot and galvanostatic charge–discharge tests. The tests results show that the ZnO/SnO2 composite exhibit the best electrochemical performances as anode material for Zn/Ni secondary batteries.