Y2O3 has a relatively high dielectric constant (13–17) leading to several potential applications. In this work, pulsed-laser deposition was used to grow epitaxial Y2O3 films on Si(111) substrates. Structural characterization indicated two-dimensional growth without the formation of an amorphous interfacial layer. Annealing in either Ar or O2 was found to induce an O2 diffusion reaction resulting in the formation of two interfacial amorphous layers. Electrical characterization by capacitance–voltage and current–voltage indicated that the as-grown samples were poor insulating films. Annealing the samples improved the electrical performance by lowering leakage currents and exhibiting inversion during capacitance–voltage testing. This epitaxial growth points toward the possibility of the heteroepitaxial growth of silicon on insulator device structures. © 2000 American Institute of Physics.