Thin films of TieZreV alloy have been deposited using an indigenously developed DC magnetron sputtering system. The microstructure of the deposited films investigated by GIXRD, AFM and FESEM exhibited a morphology that depended on substrate and deposition environment. Films deposited on stainless steel (SS) substrates in argon ambient exhibited a columnar growth with nanocrystalline grains of about 40 nm. The films were also studied using the X-ray photo-emission electron spectroscopy (XPS) after annealing them in-situ at different temperatures for two hours in ultra-high vacuum environment. The results observed through variations in the oxidation state showed that the heat treatment in vacuum leads to disappearance of the superficial oxide layer covering the TieVeZr films. After heating at 180°C the metal-oxides changed into metallic surface that was extremely conducive to adsorption of surrounding gaseous species followed by their absorption or chemical fixation. The studies suggest that the films deposited on SS substrates are suitable as a Non-Evaporable Getter (NEG) to achieve extreme high vacuum (XHV).