N-doped carbon/V2O3 microfibers as a prospective cathode material of rechargeable aqueous zinc-ion batteries are synthesized via an electrostatic spinning method followed by a high temperature carbonization process. V2O3 nanoparticles with a tunnel-like 3D crystal structure are homogeneously distributed in the N-doped carbon skeleton. N-doped C skeleton takes on an amorphous form with some structural defects. These unique structural features endow N-doped C/V2O3 electrodes with an exceptional initial discharge capacity of 459.9 mAh g−1 at 0.1 A g−1, and the capacity retention can reach to 92.95% after 152 cycles. When the current density increases to 10 A g−1, this N-doped C/V2O3 cathode delivers a larger discharge capacity of 322.3 mAh g−1 with a capacity degradation of merely 0.002% per-cycle after 4000 cycles. In addition, this N-doped C/V2O3 cathode also possesses a superior rate capability.