Biopolymer-based triboelectric nanogenerators (B-TENGs) represent an innovative fusion of eco-friendly, sustainable energy-harvesting technology with renewable and environmentally benign biopolymer material. This integration not only introduces novel pathways for advancing green energy solutions but also offers a critical approach to addressing contemporary environmental challenges and fostering sustainable progress. Over the past few years, B-TENGs have seen rapid and remarkable growth in the realm of biopolymers, device architecture, and their applications (e.g., implantable power source, electronic medicine, human anatomical and physiological movements monitoring sensors, etc.). In this review article, the promising developments in harnessing triboelectric biopolymers are encapsulated, enumerate their representative applications, evaluate the pros and cons of these biopolymers, highlight key challenges for future research, and offer strategic recommendations for innovating and realizing advanced B-TENGs.