As direct epitaxy of crystalline LaAlO3 on silicon has not been realized yet, we investigated the use of a template between the high-κ and the substrate. We performed calculations in the Density Functional Theory framework for two possible templates: a Sr0.5O monolayer and a 0.5 nm thick γ-Al2O3(0 0 1) layer. We firstly found that in the Sr0.5O monolayer case, care must be taken for the LaAlO3 starting sequence in order to expect good band offsets with silicon. In the γ-Al2O3 case, a more complex engineering of the interface is needed. Nonetheless, we found stable interfaces and a surface reconstruction in agreement with experimental observations. Moreover, these interfaces exhibit insulating properties and insight calculations for a Si–γ-Al2O3–LaAlO3 superstructure lead us to a 1.9 eV conduction band offset.