The properties of V2O5 semiconductor nanowires have been investigated using ultrashort transient absorption spectroscopy in conjunction with time resolved photoluminescence. Femtosecond pulse excitation has been utilized to generate non equilibrium carrier densities above the band edge of the Nanowires (NWs), and non-degenerate pump probe techniques have been employed to follow carrier relaxation through the conduction band and defects states located within the band gap of the semiconductor NWs. Photoluminescence revealed three relaxation mechanisms with time constants ranging from a single to tens of ns providing evidence of the importance of radiative and non-radiative decay channels associated with states within the nanowires.