Vanadium pentoxide can undergo a reversible phase transition by heating above 260 degrees C; its non-thermal phase transition, as well as ultrafast dynamical processes, is still not known. Here, femtosecond laser-induced phase transition properties in V2O5 thin films were first explored using femtosecond time-resolved pump-probe spectroscopy. The results show that the phase transient processes occur on a 10(-15)-10(-13) temporal scale. The phase transition and recovery properties are dependent on both the substrates and pump laser energy densities. We propose the oxygen vacancies theory to explain the results, and we provide valuable insights into V2O5 films for potential applications.