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Flax fibers, with abundant resources and a low cost, are an excellent precursor of carbon fibers for supercapacitors. At present, they are very attractive for designing electrodes with high electrochemical performance via a simple and green way. Hence, we systemically control the specific surface area and pore structure of flax-based carbon fibers by impregnating them with zinc chloride (ZnCl2) solution. The results show that the dehydration and expansion effects of ZnCl2 affect the microstructure, which is directly related to the specific capacitance. After activation, the optimized electrode exhibited the highest specific capacitance of 105 F g−1 at a current density of 1 A g−1, which has been improved by more than 10 times compared to that of pure-flax based carbon fibers. Moreover, they also show an excellent cycling stability of 98.7% after 10 000 cycles, even at a high current density of 10 A g−1. These results further demonstrate that flax-based electrodes have potential to be applied to some relevant energy storage applications in the future. [ABSTRACT FROM AUTHOR]