Epidermal electronics offer an important platform for various on-skin applications including electrophysiological signals monitoring and human–machine interactions (HMI), due to their unique advantages of intrinsic softness and conformal interfaces with skin. The widely used nondegradable synthetic materials may produce massive electronic waste to the ecosystem and bring safety issues to human skin. However, biomaterials extracted from nature are promising to act as a substitute material for the construction of epidermal electronics, owing to their diverse characteristics of biocompatibility, biodegradability, sustainability, low cost and natural abundance. Therefore, the development of natural biomaterials holds great prospects for advancement of high-performance sustainable epidermal electronics. Here, we review the recent development on different types of biomaterials including proteins and polysaccharides for multifunctional epidermal electronics. Subsequently, the applications of biomaterials-based epidermal electronics in electrophysiological monitoring and HMI are discussed, respectively. Finally, the development situation and future prospects of biomaterials-based epidermal electronics are summarized. We expect that this review can provide some inspirations for the development of future, sustainable, biomaterials-based epidermal electronics.