It is extremely challenging to significantly increase the voltaic efficiency, power density, and cycle stability of a Zn–air battery by just adjusting the catalytic performance of the cathode with nanometers/atomistic engineering because of the restriction of thermodynamic equilibrium potential. Herein, inspired by solar batteries, the S-atom-bridged FeNi particles and N-doped hollow carbon nanosphere composite configuration (FeNi-S,N-HCS) is presented as a prototype of muti-functional air electrode material (intrinsic electrocatalytic function and additional photothermal function) for designing photoresponsive all-solid-state Zn–air batteries (PR-ZABs) based on the photothermal effect. The local temperature of the FeNi-S,N-HCS electrode can well respond to the stimuli of sunlight irradiation because of their superior photothermal effect. As expected, under illumination, the power density of the as-fabricated PR-ZABs based on the FeNi-S,N-HCS electrode can be improved from 77 mW cm–2 to 126 mW cm–2. Simultaneously, charge voltage can be dramatically reduced, and cycle lifetime is also prolonged under illumination, because of the expedited electrocatalytic kinetics, the increased electrical conductivity, and the accelerated desorption rate of O2 bubbles from the electrode. By exerting the intrinsic electrocatalytic and photothermal efficiency of the electrode materials, this research paves new ways to improve battery performance from kinetic and thermodynamic perspectives.