In this work, pyroelectric materials can spontaneously polarize and generate an internal electric field when heated, and the photocatalyst will have band bending under the action of the internal electric field, which promotes the separation of photogenerated carriers. When HCN@PVTC@CdS is used as a photocathode pole, due to the presence of internal electric field generated by pyroelectric effect, the photocatalyst attached to the pyroelectric material will be affected, and its energy band will bend, which is conducive to the separation of photogenerated charge carriers, accelerating the reaction kinetics of the battery. Display omitted Zinc–air battery as one of the new generations of battery system, its theoretical specific energy is as high as 1086 Wh kg−1, specific capacity up to 820 mAh/g, and zinc has the advantages of environmental friendliness, resource abundance, low cost and good safety, so it has attracted much attention. However, due to its slow reaction kinetic process, zinc–air battery will produce a large charging overpotential usually up to 2 V, it is far beyond the theoretical voltage of 1.65 V, so reducing the overpotential of zinc–air batteries is extremely necessary, and the most common way to solve this problem is to use excellent catalyst cathode to improve the oxygen reduction and oxygen evolution kinetics of zinc–air batteries. So we developed a new photothermal assisted zinc–air battery system with Hollow carbon nanosphere@poly (vinylidene fluoride-trifluoroethylene-chlorofluoroethylene)@CdS(HCN@PVTC@CdS) photocathode, the pyroelectric and photocatalysis effect can effectively promote the reaction kinetics and reduce the reaction overpotential. With the pyroelectric and photocatalysis synergistic effect, the zinc–air has displayed a high discharge potential of 1.33 V and a low charging potential of 1.5 V with good cycle stability. This multi-assist technology with built-in electric and light fields paves the way for the development of high-performance zinc–air batteries and other energy storage systems.