To promote the energy density of symmetric all-solid-state supercapacitors (SCs), efforts have been dedicated to searching for high-performance electrode materials recently. In this paper, vanadium nitride (VN) nanofibers with mesoporous structure have been fabricated by a facile electrospinning method. Their crystal structures and morphology features were characterized by X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. The mesoporous structure of VN nanofibers, which can provide short electrolyte diffusion routes and conducting electron transport pathways, is beneficial to their performance as a supercapacitor electrode. Under a stable electrochemical window of 1.0 V, VN nanofibers possess an excellent mass specific capacitance of 110.8 F/g at a scan rate of 5 mV/s. Moreover, the VN nanofibers were further assembled into symmetric all-solid-state SCs, achieving a high energy density of 0.89 mW·h/cm 3 and a high power density of 0.016 W/cm 3 over an operating potential range from 0 to 1.0 V. These results demonstrate that VN nanofibers could be potentially used for energy storage devices.