Herein, a trimetallic Ni-Co-Zn perovskite fluoride (ABF 3 ) (denoted as KNCZF) electrode material is explored for advanced aqueous supercabatteries (ASCBs), with KNCZF and activated carbon-FeBiCu@reduced graphene oxides (AC-FeBiCu@rGO) as cathode and anode, respectively, which outperform aqueous supercapacitors (ASCs) and batteries (ABs) with AC and FeBiCu@rGO anodes because of the synergistic effect of pseudocapacitive (KNCZF), capacitive (AC), and faradaic (FeBiCu@rGO) responses. One of the important findings is that the KNCZF shows a typical bulk phase conversion mechanism for charge storage in the alkaline media with the transition of ABF 3 perovskite nanocrystals into amorphous metal oxides/(oxy)hydroxides nanosheets, showing the redox-active and redox-inert roles for the Ni/Co and Zn species, respectively, which can be deduced by various ex-situ techniques. Another interesting finding is that the redox-inert Zn species largely enhance the activity of Ni/Co redox-active species in the ABF 3 materials, mainly owing to the promotion of surface electroactive sites, adsorption of OH − , and charge transfer of surface Ni/Co atoms by Zn-doping, which can be proved by ex-situ characterizations and theoretical calculations. Overall, this study reveals the structure-activity relationship and charge storage mechanisms of Zn-doping ABF 3 materials for advanced ASCBs, showing a great impact on developing advanced electrochemical energy storage.