We report on the growth of high-permittivity (k) TiO2 thin films on In0.53Ga0.47As channels by chemical beam deposition with titanium isopropoxide as the source. The films grew in a reaction-limited regime with smooth surfaces. High-resolution transmission electron microscopy showed an atomically abrupt interface with the In0.53Ga 0.47As channel that indicated that this interface is thermally stable. Measurements of the leakage currents using metal-oxide-semiconductor capacitors with Pt top electrodes revealed asymmetric characteristics with respect to the bias polarity, suggesting an unfavorable band alignment for CMOS applications. X-ray photoelectron spectroscopy was used to determine the TiO2/In0.53Ga0.47As band offsets. A valence band offset of 2.5 ± 0.1 eV was measured.