The scope of this chapter is to introduce a highly efficient HfO2 atomic layer deposition (ALD) process with superior interface defect characteristics that can be applied on high-mobility III-V substrates. For a long time, the major academic research of III-V metal-oxide-semiconductor (MOS) studies was mainly oriented on searching for the suitable high-k dielectric, and among the reported high-k/III-V MOS studies, Al2O3 and AlN have demonstrated the most promising results. However, usually, the dielectrics with higher dielectric constant suffered from more defective interface quality including the HfO2, which should be overcome to meet the intensive operation voltage scaling requirements. In order to protect the interface of the HfO2/III-V MOS, the exposed III-V surface has to be carefully treated before, while, and after the whole high-k deposition process. For this purpose, the effect of isopropyl alcohol precursor and in situ cyclic nitrogen plasma treatment on the HfO2 ALD process at III-V substrates was thoroughly investigated. Remarkable interface state density levels with strong inversion behavior were achieved, which have not been observed at the previous HfO2/InGaAs studies. Also, detailed analysis of the interface characteristics was investigated to broaden the understanding of the improvement phenomenon.