a-Nickel hydroxide codoped with Al 3+ and Ca 2+ was prepared by chemical coprecipitation method. The phase structure and surface morphology of the prepared samples were characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). The electrochemical performances of the prepared samples were analyzed by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and charge/discharge tests. XRD and SEM tests reveal that the Al 3+ /Ca 2+ codoped a-nickel hydroxide has a relatively good crystallization and a very coarse surface. Electrochemical tests show that the Al 3+ /Ca 2+ codoped a-nickel hydroxide has higher proton diffusion coefficient, lower electrochemical reaction resistance, and higher discharge capacity (395.3 mAh g −1 at 0.2 C) than the Al 3+ singly doped a-nickel hydroxide, which indicates its potential application as an electrode material for secondary alkaline batteries.