A comprehensive study of the band alignments of TixAl1-xOy (with x = 9%, 16%, 25%, 36%, 100%) and GaxAl1-xOy (x = 5%, 20%, 80% and 95%) fabricated using atomic layer deposition on GaN has been presented using X-ray photoelectron spectroscopy and variable angle spectroscopic ellipsometry. The permittivity, k, has been found to be enhanced from ~10 for 9% Ti in TixAl1-xOy to 76 for TiO2, however TiO2 brings an unfavorable band alignment and a small conduction band offset (< 0.1 eV) with GaN. The latter has been observed for all studied TixAl1-xOy films deposited on GaN. On the other hand, GaxAl1-xOy films show a substantial increase of the band gap from 4.5 eV for Ga2O3 to 5.5 eV for x = 20% Ga and 6.0 eV for x = 5% Ga. A strong suppression of leakage current in associated GaxAl1-xOy-based metal insulator semiconductor capacitors has also been observed, showing promise for device applications.