Abstract: Since poly(3, 4-ethylenedioxythiophene) (PEDOT) has advantages of flexible stretchable, high biocompatibility, and controllable conductivity and work function, it has emerged extensive application prospects in the flexible wearable electronic devices. In recent years, as the increasingly resources crisis, research and development of the high efficient, green, and sustainable bio-based dopant for PEDOT: PSS (polystyrene sulfonate) system has attracted serious concerns of the relevant researchers. For the first time, this work reported a new approach to prepare high-performance PEDOT conductive film using biomass-derived aromatic weak acid, i.e., gallic acid (GA, pKa of 4.41). Its special structure of adjacent multiple phenolic hydroxyl groups created a stable dual-hydrogen bonds combination with PSSH. The binding energy of GA-PEDOT is significantly higher than that of its petroleum-based strong acidic isomer (2, 4, 6-trihydroxybenzoic acid with pKa of 1.68, ) with PEDOT. GA doping not only realized the high efficient phase separation of PEDOT-PSS, but also optimized the conformational of PEDOT molecular chain, the optimal morphology and orientation of aggregation structure. This endowed GA with high doping efficiency, and the conductivity of PEDOT conductive film can be upgraded by three orders of magnitude to 1050 S/cm, only with 1.2% of doping amount of GA. That has reached the highest conductive feature in all reported bio-based dopants, and the doping efficiency of GA is significantly higher than that of bio-based dopant and its petroleum-based strong acidic isomer.