By using an adaptively coupled plasma system, the etching rate of HfAlO3 thin films and their selectivity to SiO2 thin films were investigated as a function of gas mixture ratio. The chemical reaction on the surface was investigated by X-ray photoelectron spectroscopy (XPS). From the results, we can discern that the etching of HfAlO3 thin films follows the ion-assisted chemical etching. Moreover, Hf and Al on the surface were removed by chemical reactions with the Cl radicals, and by physical bombardments.