In the present work, the synthesis of V2O5 nanorods were exploits household microwave oven with an operating frequency of 2.45GHz. This affordable method is viable to prepare the tiny (gram) quantity of nanoparticles. The influence of annealing temperature on structural, optical and electrical properties of prepared samples has been investigated. The structural studies reveal that the crystal structure is changed from anorthic to orthorhombic phase during the annealing process. The intensity of X-ray diffraction peak at 2θ=34° is strongly dependent on the structure of V2O5 sample with preferred orientation along (002) c-axis. The hexagonal face rods with thickness of few nanometers were confirmed by SEM/TEM results. Temperature dependent DC conductivity was carried out and the respective electrical conduction mechanism is established by thermal activation of conduction electrons. Further, the colloidal form of V2O5 nanopowders have been deposited on p-Si substrate for the p-n junction formation by the nebulizer spray technique. The voltage-current characteristics of established diodes have been studied through dark and under illumination conditions. Besides, the photoresponse of developed diodes have been confirmed by the transient photocurrent measurement.