In this work, Ni(OH)2 and (BiO)4CO3(OH)2 microspheres are synthesized by solvothermal method. Then, a novel alkaline rechargeable Ni/Bi battery is assembled for the first time using the synthesized Ni(OH)2 and (BiO)4CO3(OH)2 as the positive electrode and negative electrode materials, respectively. As a result, the assembled Ni/Bi battery delivers a high specific capacity of 113 mAh g−1 at a discharge rate of 0.2C based on the total mass of the electrode materials, as well as a high energy density of 92 Wh kg−1 at a power density of 27.3 W kg−1.