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Porous carbon nanofibers (PCNFs) have been the hotpot material for supercapacitor due to their porous structure, outstanding conductivity, excellent electrochemical properties, and high specific surface area. The template method is a facile approach to prepare PCNFs through blending a thermally decomposable substance, subsequently heating treatment. High amylose starch (HAS) is a natural carbohydrate including carbon, hydrogen and oxygen elements. Herein, a simple template method utilizing HAS as the sacrificial polymer to prepare porous carbon nanofibers with high specific surface areas has been reported. The resulted carbon nanofibers have a hierarchical micro/meso porous structure with high level of microporous pores, more importantly, their specific surface area can reach 1204 m2 g−1. The electrochemical performances of PCNFs electrodes are studied using a three-electrode system and button-type devices. The specific capacitance of carbon nanofiber electrode is 344 F g−1 at 1.0 A g−1 when 20 wt% HAS is added. The cycling durability of corresponding device is 99.9% capacitance retention after 10000 cycles. And the maximum energy density of 12 Wh kg−1 is obtained at a lower power density of 125 W kg−1. As a green natural material, HAS may provide a low-cost solution to prepare high-performance carbon nanofibers for energy storage applications. [Display omitted] • An in-situ activation method is used to prepare hierarchical micro/meso porous carbon nanofibers. • High amylose starch can be as a sacrificial polymer to prepare carbon nanofiber with a high specific surface area. • Supercapacitor electrodes prepared from the carbon nanofibers show large specific capacitance and excellent durability. [ABSTRACT FROM AUTHOR]