Zn/MnO2 batteries including an ionic liquid-based gel polymer electrolyte (IL-GPE) have been discharged or discharged and then recharged reaching different states of charge. The Zn electrodes used in these Zn/MnO2 batteries are studied by HAXPES and synchrotron XRD techniques. Besides, HAXPES measurements are compared with the results obtained by a conventional XPS. Formation of Zn(OH)2 and ZnO is found in intermediate states of charge during charging and discharging. However, only ZnO is observed in the anode when a full discharging was carried out. Conversely, an entire charging process produces a complete reduction of all Zn2+ species to metallic Zn. In addition, various techniques have confirmed the entrance of Triflate anions and NMP solvent molecules in the electrode, accompanying the Zn2+ cations movement during the charging.