The metal gate/high-k dielectric/III-V semiconductor band alignment is one of the most technologically important parameters. We report the band offsets of the Al/Al2O3/GaAs structure and the effect of GaAs surface treatment. The energy barrier at the Al2O3 and sulfur-passivated GaAs interface is found to be 3.0±0.1 eV whereas for the unpassivated or NH4OH-treated GaAs is 3.6 eV. At the Al/Al2O3 interface, all samples yield the same barrier height of 2.9±0.2 eV. With a band gap of 6.4±0.05 eV for Al2O3, the band alignments at both Al2O3 interfaces are established.