Bi-doped Zn-Al layered double hydroxides (Zn-Al-Bi LDH) are prepared by the constant pH hydrothermal method and proposed as a novel anodic material in Zn/Ni secondary cells. The Fourier transform infrared spectra (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM) images reveal that the as-prepared samples are well-crystallized and hexagon layer structure. The electrochemical performances of the Zn-Al-Bi LDH were analyzed by cyclic voltammetry, tafel plot, electrochemical impedance spectroscopy (EIS) and galvanostatic charge-discharge tests. Compared with Zn-Al LDH, Zn-Al-Bi LDH with different Zn/Al/Bi molar rations, especially the sample of Zn/Al/Bi=3:0.8:0.2 (molar ration) have higher discharge capacity and more stable cycling performances. Cyclic voltammograms clearly illuminated that the Zn-Al-Bi LDHs could decrease polarization, maintain the electrochemical activity, and enhance the discharge capacity of Zn-Al LDH. This battery can undergo at least 800 charge-discharge cycles at constant current of 1C without dendrite and short circuits. The discharge capacity of Zn-Al-Bi LDH after the 800th cycle remains about 380mAhg−1 and the hexagonal crystal structure have no much changed after cycles.