We report the epitaxial growth of γ-Al2O3 on SrTiO3 (STO) substrates by atomic layer deposition (ALD). The ALD growth of γ-Al2O3 on STO(001) single crystal substrates was performed at a temperature of 345 °C. Trimethylaluminum and water were used as co-reactants. In-situ reflection high-energy electron diffraction and ex-situ x-ray diffraction were used to determine the crystallinity of the Al2O3 films. In-situ x-ray photoelectron spectroscopy was used to characterize the Al2O3/STO heterointerface. The formation of a Ti3+ feature is observed in the Ti 2p spectrum of STO after the first few ALD cycles of Al2O3 and even after exposure of the STO substrate to trimethylaluminum alone at 345 °C. The presence of a Ti3+ feature is a direct indication of oxygen vacancies at the Al2O3/STO heterointerface, which provide the carriers for the quasi-two dimensional electron gas at the interface.