In this work, the atomic layer deposition process using ozone and trimethylaluminum (TMA) for the deposition of Al2O3 films on WSe2 was investigated. It was found that the ozone-based atomic layer deposition enhanced the nucleation of Al2O3 in comparison to the water/TMA process. In addition, the chemistry at the Al2O3/WSe2 interface and the surface morphology of the Al2O3 films exhibited a dependence on the deposition temperature. A non-covalent functionalizing effect of ozone on WSe2 at low deposition temperatures 30 °C was identified which prevented the formation of pinholes in the Al2O3 films. These findings aim to provide an approach to obtain high-quality gate dielectrics on WSe2 for two-dimensional transistor applications.