β-CoOOH coated spherical β-NiOOH powders were synthesized as the positive electrode material for a new type of alkaline Zn-NiOOH battery. The scanning electron microscope (SEM), X-ray diffraction (XRD), inductively coupled plasma-atomic emission spectroscopy (ICP-AES), storage stability and electrochemical properties of the samples were investigated. The results showed that the β-CoOOH coated spherical β-NiOOH exhibited superior electrochemical performance and storage stability than uncoated spherical β-NiOOH. AA size alkaline Zn-NiOOH batteries were assembled by directly using β-CoOOH coated spherical β-NiOOH as the positive electrode material. The discharge–charge experiments revealed that the alkaline Zn-NiOOH battery displayed longer discharge time and higher discharge voltage than the conventional alkaline Zn-MnO2 battery under heavy load. Moreover, the Zn-NiOOH battery can be used not only conveniently as primary battery but also repeatedly as rechargeable battery.