V2O5/Al2O3 nanocomposites were synthesized by the wet chemical method, using mixed solvents such as water/ethanol and water/ethylene glycol (EG). The XRD results confirmed the crystalline nature and the presence of the orthorhombic structure of V2O5 and hexagonal phase of α-Al2O3 nanocomposites. Transmission electron microscopy (TEM) analysis showed the agglomerated cluster nanoparticles in water/ethanol mediated V2O5/Al2O3 nanocomposite; whereas well dispersed spherical nanoparticles with controlled particle size in water/ethylene glycol mediated V2O5/Al2O3 nanocomposite. The Fourier transform infrared (FTIR) results confirmed the formation of a VO and AlO bond. Photoluminescence (PL) studies revealed that V2O5/Al2O3 nanocomposites contain high intense peaks in the UV and visible region which are likely to have originated from the oxygen vacancies; and are potential material for electronic device applications and catalytic activities. The band gap energies of the samples prepared for water/ethanol and water/ethylene glycol obtained by the tauc plots are 3.6 and 3.62 eV respectively.