Lightweight green polymer materials with exceptional toughness, high strength, and excellent ductility represent ideal candidates for enabling next-generation sustainable flexible electronics. However, the conflicting properties of material strength and toughness present a significant challenge in achieving an optimal combination of both attributes. In this study, a strong yet tough polymeric triboelectric material is prepared by constructing a multiscale reinforced network based on a nonsolvent-induced microphase separation strategy. The synergistic enhancement of strength and toughness is achieved by reinforcing non-covalent interactions within the polymer and constructing nanofibrous networks. The resulting triboelectric materials exhibited remarkable fracture toughness (78.6 MJ m−3), high tensile strength (42.5 MPa), an improvement in triboelectric output (71%), and promising recyclability. The integrated triboelectric wearable sensor maintained robust output signals. This study provides a novel solution for coordinating the conflicts between strength and toughness in heterogeneous polymer materials, showing significant potential in expanding their applications in flexible electronics and self-powered sensing technologies.