Due to their good wearability, smart fabrics have gradually developed into one of the important components of multifunctional flexible electronics. Nevertheless, function integration is typically accomplished through the intricate stacking of diverse modules, which inevitably compromises comfort and elevates processing complexities. The integration of these discrete functional modules into a unified design for smart fabrics represents a superior solution. Here, we put forward a rational approach to functional integration for the typical challenges of thermal management, energy supply, and surface contamination in smart fabrics. This sandwich-structured multilayer fabric (MLF) is obtained by continuous electrospinning of two layer P(VDF-HFP) fabric and one layer P(VDF-HFP) fabric functionalized with core–shell SiO2/ZnO/ZIF-8 (SZZ) nanoparticles. Specifically, MLFs achieve effective and stable energy harvesting in triboelectric nanogenerators (TENGs) with hydrophobicity and antibacterial properties. Meanwhile, MLFs also have high mid-infrared emissivity and sunlight reflectivity, successfully realizing radiative cooling under different climates, and have been applied in wearing clothing, roof shading, and car covers. This work may contribute to the design and manufacturing of next-generation thermal comfort smart fabrics and wearable electronics, particularly in terms of the rational design of multifunctional devices.