The electrolyte carbonation and the resulting air electrode plugging are the primary factors limiting the cycle life of aqueous alkaline zinc–air batteries (ZABs). In this work, calcium ion (Ca2+) additives were introduced into the electrolyte and the separator to resolve the above issues. Galvanostatic charge–discharge cycle tests were carried out to verify the effect of Ca2+on electrolyte carbonation. With the modified electrolyte and separator, the cycle life of ZABs was improved by 22.2% and 24.7%, respectively. Ca2+was introduced into the ZAB system to preferentially react with CO32−rather than K+and then precipitated granular CaCO3prior to K2CO3, which was deposited on the surface of the Zn anode and air cathode to form a flower-like CaCO3layer, thereby prolonging its cycle life.