Phase pure and Al3+ doped vanadium pentoxide nanostructure materials (AlxV(2-x)O5(x = 0, 0.01, 0.03 and 0.05)) have been synthesized by surfactant-free non-hydrolytic sol-gel route. The effect of dopant concentration on structural, morphological, elemental, luminescence and electrochemical properties was studied for the prepared samples. XRD analysis shows that all the samples possess orthorhombic structure in nature. HRSEM and HRTEM images of Al3+ doped V2O5 nanostructures revealed the morphology of self-assembled nanorods. The presence of elements, V, Al and O with their oxidation states was ensured by FTIR, EDXS and XPS analyses. The DRS-UV-vis and PLE spectral analyses exhibit that the optical band gap of Al:V2O5 nanostructure materials increases with increase in dopant concentration. The CV results reveal that the product has a better cyclic performance and might act as a primary cathode material for high energy density secondary lithium ion batteries. © 2018 IOP Publishing Ltd.