AbstractThe developments of natural biomaterials‐based triboelectric nanogenerators (TENGs) have been emerged with the extensive and promising requirements in biomedical and biowearable fields due to the properties of renewability, cost‐effectivity, biocompatibility, and biodegradability. In this work, a flexible, recyclable, and high‐performance pullulan‐based TENG, fabricated with pullulan and other additives, is developed. Based on the open‐circuit voltage, the thickness and the additives of pullulan‐based TENGs are optimized. The maximum open‐circuit voltage, 79 V, under 10 Hz motion frequency and 10 W loading power is obtained in the NaF‐pullulan TENG. And the optimal output power density is 41.7 mW m−2 under 7 MΩ loading resistance. Then, practical applications of the as‐fabricated pullulan‐based TENGs on lighting LED arrays and monitoring hand bending movements are successfully investigated, presenting the feasibility of powering electric devices and acting as wearable devices. Finally, the excellent recyclability of the P‐P film is illustrated by the excellent TENG performance within five‐times recycles. Thus, the recyclability and facile fabrication procedures of the pullulan‐based TENGs could provide a potential prospect in the next‐generation biowearable devices and energy harvesters.