Tantalum pentoxide (Ta2O5) thin films were synthesized using thermionic vacuum arc (TVA) technology. TVA is an original deposition method using a combination of anodic arc and electron gun system for the growth of thin films from solid precursors under vacuum of 10−6 Torr. The properties of the deposited Ta2O5 thin films were investigated in terms of wettability, refractive index, morphology, and structure. The surface free energy was determined by means of surface energy evaluation system indicating a hydrophilic character and the refractive index was measured by Filmetrics F20 device. The morphology was determined from bright field transmission electron microscopy (TEM) image performed by Philips CM 120 ST TEM system. It exhibits nanoparticles of 3–6 nm diameter smoothly distributed. Selected area electron diffraction pattern revealed the contrast fringes given by complex polycrystalline particles included in the amorphous film. The measured fringes could be indexed using monoclinic structure of Ta2O5.