The composite of graphene oxide (GO) and polyaniline (PANI) is a promising electrode material for supercapacitors. A high loading of PANI can provide large specific capacitance, but it is a pervasive challenge to reconcile long-term cycling stability and high-rate discharge. Herein, we focus on a GO/PANI composite with low PANI content (∼25 wt%), developing a stable network of GO with an even distribution of PANI. Moreover, significantly enhanced electrochemical performance is achieved by utilizing plasma technology. The specific capacitance increases by 99 % to 433 F g−1 at 1.5 A g−1 after Argon (Ar) plasma treatment. Even at 15 A g−1, a capacitance retention rate of 91 % is obtained. After 15,000 cycles, the capacitance retention rate is 93 %, surpassing most previously reported GO/PANI composite electrodes. The further assembled all-solid-state supercapacitors can deliver a high energy density of 13.6 Wh kg−1 and exceptional cycling stability. According to results of characterization, it is demonstrated that Ar plasma imparts GO/PANI better surface morphology and achieves etching, reduction of GO, and cross-linking of GO and PANI, thereby activating the electrochemical activities of GO and PANI while ensuring stability. In this regard, the synergistic effects of cross-linking, reduction, and etching, and the mechanism are theoretically illustrated by dynamic differential equations. This work presents plasma processing unique charm for designing graphene-based materials via a customized strategy, exploiting an effectual approach to drive the applications of graphene-based materials in energy storage.