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In this study, TiO2 nanostructured coatings on Ti-6A-4V alloys were fabricated by two methods: H2O2 oxidation and RF sputtering. In the annealing temperature range of 25 C - 500 C, there were the peaks at 35, 37, 40 and 52 corresponding to {100}, {002}, {101} and {102} crystal planes of hcp structure of α-Ti. At the annealing temperature of 600 C, there was the presence of peaks corresponding to crystal planes of anatase and rutile TiO2. The relative intensities of anatase and rutile phases of the sample fabricated by RF sputtering were 3.62 and 10.25 %, respectively; while those of the sample fabricated by H2O2 oxidation were 21.27 and 3.20 %, respectively (The relative intensity of α-Ti phase was 100 %). The results investigated the peak shift of α-Ti phase in TiO2/Ti-6Al-4V nanostructured coatings fabricated by the two methods which was reasonably explained from the difference in the thermal expansion coefficients of Ti alloy and TiO2 components, as well as the difference in the ratio of anatase to rutile phases.