Bioenzyme-catalyzed conductive polymer polymerization is an ecological and environmental protection method that aligns with the current sustainable development plan. Hence, a new strategy of in situ assembly of poly (3,4-ethylenedioxythiophene) (PEDOT) on the surface of fabrics via free radical polymerization initiated by the cascade reaction of glucose oxidase (GOx) and horseradish peroxidase (HRP) was introduced. With excellent photothermal conversion capability and sensitive humidity response, PEDOT endows the fabric with remarkable photothermal performance, humidity sensing performance, and UV resistance capability. It is worth noting that the PEDOT-coated fabric can reach a fantastic 54.2 °C within 20 s under 2 sun irradiation intensity and finally reach 98.4 °C. In addition, it can maintain stable and fast responses in repeated and long-term operations. Moreover, the PEDOT-coated fabric has a fast response and long-term working ability in high humidity. This work provides a new environmental protection and sustainability idea for designing and developing conductive polymer-based high-performance composites.