New forms of vanadium oxide Nanoporous were fabricated using a simple chemical synthesis method. Vanadium pentoxide (V2O5) Nanoporous were synthesized by sodium metavanadate as precursor and ethylene glycol as surfactant. The samples were characterized by high resolution transmission electron microscopy (HRTEM), field effect scanning electron microscopy (FESEM) and X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and UV-Vis spectrophotometer. Structures of the nanoparticles were characterized by XRD technique to identify α-vanadium and γ-vanadium. The smallest particle size of sponge-like as-prepared sample was around 20 nm in diameter and for annealed sample was around 25 nm as estimated by XRD technique and direct HRTEM observation. The surface morphological studies from SEM depicted increasing dimension of sponge-like shaped structure by increasing ratio of the EG surfactant from 25 nm to 30 nm. The sharp peaks in FTIR spectrum determined the purity of V2O5 nanoparticles.