The electrical properties of ultrathin amorphous Al2O3 films, grown by low temperature metal-organic chemical vapor deposition from aluminum(III) 2,4-pentanedionate and water as co-reactants, were examined for potential applications as gate dielectrics in emerging complementary metal-oxide semiconductor technologies. High-frequency capacitance–voltage and current–voltage techniques were used to evaluate Al2O3 films deposited on silicon oxynitride on n-type silicon (100) substrates, with thickness ranging from 2.5 to 6.5 nm, as a function of postdeposition annealing regimes. Dielectric constant values ranging from 11.0 to11.5 were obtained, depending on the annealing method used. Metal-insulator-semiconductor devices were demonstrated with net equivalent oxide thickness values of 1.3 nm. Significant charge traps were detected in the as-deposited films and were mostly passivated by the subsequent annealing treatment. The main charge injection mechanism in the dielectric layer was found to follow a Poole–Frenkel behavior, with post-annealed films exhibiting leakage current an order of magnitude lower than that of equivalent silicon oxide films.