AbstractHigh‐output triboelectric nanogenerators (TENGs) are demonstrated based on polyimide (PI)‐based polymers by introducing functionalities (e.g., electron‐withdrawing and electron‐donating groups) into the backbone. The TENG based on 6FDA‐APS PI, possessing the most negative electrostatic potential and the low‐lying lowest unoccupied molecular orbital level, produces the highest effective charge density of about 860 µC m−2 in practical working conditions with the ion injection process. This may be ascribed to the excellent charge‐retention characteristics as well as the enhanced charge transfer capability, which increases the output power by 7 times compared to the commercially available Kapton film‐based TENG. Finally, a 6FDA‐APS‐driven sensor network system is demonstrated, providing the identity of three gases (H2, CO, and NO2) by illuminating the light‐emitting diodes within several seconds.