Prussian blue analogs (PBAs) are considered as reliable and promising cathode materials for aqueous Zn‐ion batteries (AZIBs), but they suffer from low capacity and poor cycling stability due to insufficient active sites and structural damage caused by the ion insertion/extraction processes. Herein, a template‐engaged ion exchange approach has been developed for the synthesis of Co‐substituted Mn‐rich PBA hollow spheres (CoMn‐PBA HSs) as cathode materials for AZIBs. Benefiting from the multiple advantageous features including hollow structure, abundant active sites, fast Zn2+ ion diffusion, and partial Co substitution, the CoMn‐PBA HSs electrode shows efficient zinc ion storage properties in terms of high capacity, decent rate capability and prolonged cycle life. Co‐substituted Mn‐rich Prussian Blue Analog (PBA) hollow spheres (CoMn‐PBA HSs) are rationally designed and synthesized through an efficient self‐templating approach. Benefiting from the hollow structure and partial Co substitution, the CoMn‐PBA HSs electrode exhibits enhanced zinc ion storage performance with high capacity, favorable rate capability, and impressive cycling stability.