Given health threat by global warming and increased energy consumption in regulating body temperature, it is an urgent need to construct smart temperature-regulating materials. Herein, a novel fiber-spinning asymmetric chemical assembly (FACA) method is proposed to construct nanofiber materials with asymmetric photothermal properties. The silver nanowires (AgNWs) and poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) with opposite thermal radiation are assembled on reduced graphene oxide (rGO) film, imparting AgNW/rGO/PVDF-HFP film with Janus structure that can realize the AgNWs side consistently keeps temperature of ca. 11 °C lower than the side of PVDF-HFP nanofiber regardless of the irradiation directions under 1 sun, suggesting the adjustable photothermal regulation. Such photothermally selective hybrid nanofiber film provides great potential as fabrics to achieve all-weather smart clothes, promoting controllable and comprehensive utilization of solar energy.