The synthesis of single crystalline divanadium pentaoxide nanoribbons using a simple thermal vapor deposition technique was reported by considering the smooth surface and high refractive index that give rise to the tight optical confinement. The representative dark-field optical-images revealed the nanofibers with a typical length of several hundred micrometers and even upto millimeters in the high yield. The experimentation employed a 457 nm laser to examine the waveguiding properties of the as-grown V2O5 nanoribbons. A clean piece of vanadium foil with a purity of 99.8% was heated at 660 °C under ambient conditions with a piece of Si wafer covering the foil without the use of catalyst. The results fully explored the optical behavior of these nanoribbons, especially with respect to their potential to exhibit nonlinear properties and sensing.