Triboelectric nanogenerators (TENGs) are versatile electronic devices used for environmental energy harvesting and self-powered electronics with a wide range of potential applications. The rapid development of TENGs has caused great concern regarding the environmental impacts of conventional electronic devices. Under this context, researching alternatives to synthetic and toxic materials in electronics are of major significance. In this review, we focused on TENGs based on natural polysaccharide materials. Firstly, a general overview of the working mechanisms and materials for high-performance TENGs were summarized and discussed. Then, the recent progress of polysaccharide-based TENGs along with their potential applications reported in the literature from 2015 to 2020 was reviewed. Here, we aimed to present polysaccharide polymers as a promising and viable alternative to the development of green TENGs and tackle the challenges of recycling e-wastes.