Polymers are playing important roles in the rapid development of triboelectric nanogenerators (TENGs); However, most polymers cannot meet the high requirements of thermomechanical performance; Thus, various polymeric composites are developed for triboelectric layer. These composites are hardly recycled since their reinforcements are unevenly distributed after reprocessing, which limits the sustainable development of TENGs. To solve the above challenges, in situ generated nanofiber reinforced composites (NFRCs) based on single-component liquid crystal polyarylate (LCP) are designed and prepared via a one-step polycondensation. Nonlinear naphthalene (NDA) widens the processing window of LCP without destabilizing the liquid crystal phase. The NDA-rich domains act as a matrix while the NDA-poor domains with higher rigidity form oriented nanofibers to achieve self-reinforcement. The resultant NFRCs possess high glass transition temperature (Tg > 220 °C) and storage modulus (E′ = 0.1 GPa at 350 °C), which are far beyond existing triboelectric polymers, typically Tg < 110 °C and E′ < 0.1 MPa (flowable) at 350 °C. Furthermore, NFRC-based TENG exhibits superior electrical output performance and retention rate (>90%) after reprocessing; Overall, this work offers a new design principle to prepare self-reinforced composites, which paves a way to explore high performance materials.