In this work, the influence of the substrate bias on the crystalline structure and surface composition of Ti6Al4V thin films prepared by rf magnetron sputtering were studied. Samples were grown onto two different types of substrates: AISI 420 steel and common glass using a Ti6Al4V (99.9 %) target. Substrate bias was varied from -100V to -200 V. Samples were characterized by X-ray diffraction (XRD), Energy Dispersive X-ray Analysis (EDX), Scanning Electron Microscopy (SEM), and X-Ray Photoelectron Spectroscopy (XPS). It was observed that the increase of the substrate voltage improved the crystallinity of the deposited films. The stoichiometry of the deposited thin films was studied by EDX and found to be slightly different from that of the target material. Finally, the passive film spontaneously formed on the deposited films upon exposure to the laboratory atmosphere was studied by XPS. The composition of the passive film is rather complex since it contains several forms of oxidized titanium and vanadium as well as Al2O3.