Extreme frictional wear of triboelectric layers severely hinders long-term sustainability of triboelectric nanogenerators (TENGs) for efficient ambient energy harvesting. The state-of-the-art solutions necessitate sophisticated structural designs and complex packaging constraints, impeding the feasibility of TENGs for practical applications. Herein, inspired by the structures and compositions of snake scales, a biomimetic composite (BC) film is fabricated as a wear-resistant triboelectric contact layer. The successful formation of disulfide bond-facilitated cross-linkage of cysteine proteins in the keratin-based BC film promotes excellent mechanical resilience and durability, thereby solving the material abrasion challenges associated with solid-solid triboelectric layers.The BC film, with toothed microstructure, exhibits improved charge transfer, low friction, and consistent long-term stable outputs compared to commercial films. Furthermore, a self-powered BC film-based TENG is integrated into a bicycle for biomechanical energy harvesting, lightening warning signals for safer night ride with stable 300   V electrical output for at least 6   hours. Moreover, a smart health monitoring system is further proposed by embedding TENG-based sensors into the bicycle saddle, accurately capturing the rider’s pelvic-saddle interactions on varying terrain slopes. By leveraging the unique biomechanical information, machine learning-assisted user identification and terrain slope data classifications are achieved with high accuracies, laying a foundation for futuristic smart healthcare applications. This work provides a strategy to reduce material abrasion by exploiting the unique characteristics of a biomimetic material, facilitating a basis for efficient environmental energy harvesting and smart sensing.