The interfacial thermal stability and band alignment of La2O3/Al2O3 nanolaminates with different terminations (LaOx and AlOx) deposited by atomic layer deposition have been investigated after annealing. Initial results indicate that the interfacial thermal stability is affected by the different terminations. An obvious formation of the interfacial layer is observed for La2O3/Al2O3 nanolaminates with LaOx termination, whereas the interfacial layer for La2O3/Al2O3 nanolaminates with AlOx termination increases negligibly after annealing. The different interfacial thermal stabilities cause different changes on the surface roughness, band offset, leakage current and C–V properties of La2O3/Al2O3 nanolaminates after annealing. A detailed analysis is performed to confirm the origin of the changes. All results indicate that La2O3/Al2O3 nanolaminate with AlOx termination can provide good dielectric properties, which is very useful for the high-κ process development.