To solve the problems of low electrical conductivity and poor stability of V2O3 as an anode electrode of secondary batteries, sulfur (S) doped V2O3/C nanowires were prepared via electrostatic spinning and sulfuration treatment technology. The structure, chemical composition, and energy storage properties were characterized. The results show that the S doped V2O3/C nanowire as an anode electrode for lithium ion batteries has a discharge specific capacity of 538 mA·h/g at a current density of 0.1 A/g after 50 cycles, and the discharge specific capacity at 2 A/g after 600 cycles can still maintain 288 mA·h/g. The specific capacity of sodium ion batteries with S-doped V2O3/C nanofiber as an anode electrode is 233 mA·h/g at 0.1 A/g after 100 cycles.