The electrical and interfacial properties of HfO2/Al2O3 and Al2O3/HfO2 dielectrics on AlN/p-Ge interface prepared by thermal atomic layer deposition are investigated by capacitance–voltage(C–V) and current–voltage(I–V) measurements. In the C–V measurements, humps related to mid-gap states are observed when the ac frequency is below 100 kHz, revealing lower mid-gap states for the HfO2/Al2O3 sample. Higher frequency dispersion in the inversion region is observed for the Al2O3/HfO2 sample, indicating the presence of slow interface states A higher interface trap density calculated from the high-low frequency method is observed for the Al2O3/HfO2 sample. The parallel conductance method, applied to the accumulation region, shows border traps at 0.3~0.32 eV for the Al2O3/HfO2 sample, which are not observed for the Al2O3/HfO2 sample. I–V measurements show a reduction of leakage current of about three orders of magnitude for the HfO2/Al2O3 sample. Using the Fowler-Nordheim emission, the barrier height is calculated and found to be about 1.08 eV for the HfO2/Al2O3 sample. Based on these results, it is suggested that HfO2/Al2O3 is a better dielectric stack than Al2O3/HfO2 on AlN/p-Ge interface.