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[Display omitted] • Acetylated sugarcane bagasse is blend electrospun with polyacrylonitrile successfully. • Hierarchically porous structure of carbon nanofiber is introduced without any activation. • As-prepared carbon nanofiber is flexible, porous, and with high capacitive performance. The biomass-based carbon nanofibers (CNFs) have been regarded as promising electrode materials for supercapacitors. However, the preparation of biomass-based hierarchically porous CNFs by electrospinning without any chemical and physical activation is still challenging, especially when using the whole components of lignocellulose. Herein, a feasible way to synthesize a hierarchically porous CNF by electrospinning of the blends of acetylated sugarcane bagasse (ASCB) and polyacrylonitrile (PAN) followed by carbonization is proposed. Degradation of ASCB during carbonization induced multiscale defects that led to the formation of hierarchical pores and introduced flexibility for the CNFs. The specific capacitance and areal capacitance of CNFs respectively were 289.5 F g−1 and 64.2 μF cm−2. The flexible all-solid-state symmetric supercapacitor (ASSC) derived from the CNFs showed high power density (1.26 kW kg−1) and energy density (56.0 W h kg−1), as well as high capacitance retention and great cycling stability. This synthetic strategy provides a practicable way to utilize the whole components of lignocellulosic biomass and explore its application on high-performance flexible electrode materials. [ABSTRACT FROM AUTHOR]