The mounting demand for sustainable, self-powered biomedical devices, particularly those engineered for extreme environments, has established triboelectric nanogenerators (TENGs) as a prominent technology in energy harvesting research. This review examines state-of-the-art biomaterial synthesis strategies essential for developing high-performance bioelectronic TENGs that can operate reliably under harsh conditions, including elevated temperatures, extreme humidity, and mechanical strain. It begins with a comprehensive overview of the fundamental principles of triboelectricity and subsequently addresses the pivotal challenges associated with efficient charge generation and retention in such challenging settings. The content places particular emphasis on recent advancements in composite material engineering and structure design for high-efficiency mechanisms, with a particular focus on biocompatible and environmentally resilient materials. The integration of TENGs into wearable sensors, implantable devices, and self-powered monitoring systems is also investigated, demonstrating their transformative potential for bioelectronic applications. Our goal subsequently underscores persistent limitations to overcome, including those pertaining to fabrication scalability and long-term operational stability, while concurrently proposing prospective research directions. Consequently, this work underscores how innovative biomaterial synthesis and bioelectronic devices can enable the development of next-generation, high-performance, self-powered devices suited for extreme biomedical environments.