The electrical properties of Al/LaAlO3/GaAs metal-oxide-semiconductor capacitors were investigated. A thick arsenic (As2) capping layer was used to protect the GaAs from oxidation and contamination during the air exposure that occurred between the deposition of the GaAs and LaAlO3 layers in different molecular-beam epitaxy systems. Amorphous LaAlO3 was deposited on c(4×4)- and (2×4)-reconstructed (100) GaAs surfaces. Post dielectric deposition annealing was found to improve the capacitance-voltage (C-V) characteristics by eliminating frequency dispersion in the depletion and weak inversion regimes and diminished the bi-directional C-V hysteresis to 210 mV. Reasonably low gate leakage current was maintained after annealing.