The influence of CeO2 additions on the electrochemical behaviour of the MnO2 cathode in a Zn–MnO2 battery using lithium hydroxide (LiOH) as an electrolyte is investigated using microscopy and spectroscopic techniques. The results showed that such additions greatly improve the discharge capacity of the battery (from 155 to 190mAhg−1) but only from the second discharge cycle onwards. Capacity fade with subsequent cycling is also greatly reduced. With an aim to understand the role of CeO2 on the discharge–charge characteristics of MnO2 and its mechanism, we have used a range of microscopy, spectroscopy and diffraction-based techniques to study the process. The CeO2 is not modified by multiple discharged and charged cycles. The CeO2 may enhance the discharge–charge performance of the battery by raising the oxygen evolution potential during charging but does not take part directly in the redox reaction.