In this work, the electrical performance and interfacial characteristics of MOCVD-grown Al2O3 films are evaluated. Electrical characteristics (dielectric constant, leakage current) of as-deposited and annealed capacitor metal-oxide-semiconductor (MOS) stacks were determined using capacitance-voltage (C-V) and current-voltage (I-V) measurements. It was observed that the electrical properties were dependent upon specific annealing conditions, with an anneal in O2 followed by forming gas being superior with respect to leakage current, resulting in leakage characteristics superior to those of SiO2. All annealing conditions evaluated led to an increase in dielectric constant from 6.5 to 9.0–9.8. Also, Al2O3 growth and interfacial oxide growth characteristics on oxynitride/Si and Si substrates were evaluated and compared using spectroscopic ellipsometry. A parasitic oxide layer was observed to form on silicon during the initial stages of MOCVD Al2O3 growth, while a thin oxynitride layer deposited on Si prevented the growth of interfacial oxide.