The ability to apply a low temperature sintering technique, so called cold sintering process, was employed to fabricate V2O5 ceramic and carbon nanofiber (CNF) composites. The densities, microstructures, as well as electrical and electrochemical properties of (1 − x)V2O5–xCNF composites cold sintered at a temperature of 120 °C for a time of 20 min were investigated. All the samples can be sintered to >85% theoretical densities by cold sintering process. There is a limited grain growth in the cold sintered (1 − x)V2O5–xCNF composites. A small amount of V2O5 amorphous phase can be observed and most of the CNFs are distributed along the grain boundaries of V2O5 ceramic. With increasing the amount of CNFs, the electrical (electrical conductivity) and electrochemical (capacity) properties of (1 − x)V2O5–xCNF composites improve accordingly.