With the growing application of high-k dielectrics, the interface between HfO2 and Al2O3 play a crucial role in CTM devices. To clearly understand the interaction of the HfO-AlO interface at the atomic and electronic scale, the bonding feature, electronic properties and charge localized character of c- HfO2 (0 0 1)/α-Al2O3 (1 -1 0 2) interface has been investigated by first principle calculations. The c- HfO2 (0 0 1)/α-Al2O3 (1 -1 0 2) interface has adhesive energy about -1.754 J/m2, suggesting that this interface can exist stably. Through analysis of Bader charge and charge density difference, the intrinsic interfacial gap states are mainly originated from the OII and OIII types oxygen atoms at the interface, and only OIII type oxygen atoms can localized electrons effectively and are provided with good reliability during P/E cycles, which theoretically validate the experimental results that HfO2/Al2O3 multi-layered charge trapping layer can generate more effective traps in memory device. Furthermore, the influence of interfacial gap states during P/E cycles in the defective interface system have also been studied, and the results imply that defective system displays the degradation on the reliability during P/E cycles, while, the charge localized ability of interfacial states is stronger than intrinsic oxygen vacancy in the trapping layer. Besides, these charge localized characters are further explained by the analysis of the density of states correspondingly. In sum, our results compare well with similar experimental observations in other literatures, and the study of the interfacial gap states in this work would facilitate further development of interface passivation.