In the present work, the oxide layers developed at elevated temperature on three vanadium-free titanium alloys, of interest as implant biomaterials, were studied by Rutherford backscattering spectroscopy, elastic recoil detection analysis, and scanning electron microscopy. The chemical composition of the alloys investigated, in wt%, was Ti–7Nb–6Al, Ti–13Nb–13Zr, and Ti–15Zr–4Nb. Upon oxidation in air at 750 °C, an oxide scale forms, with a chemical composition, morphology, and thickness that depend on the alloy composition and the oxidation time. After equal exposure time, the Ti–7Nb–6Al alloy exhibited the thinnest oxide layer due to the formation of an Al2O3-rich layer. The oxide scale of the two TiNbZr alloys is mainly composed of Ti oxides, with small amounts of Nb and Zr dissolved. For both TiNbZr alloys, the role of the Nb-content on the mechanism of the oxide formation is discussed.