jats:pPhase-change memories based on reversible amorphous-crystal transformations in pseudobinary GeTe-Sb2Te3 alloys are one of the most promising nonvolatile memory technologies. The recently proposed superlattice-based memory, or interfacial phase-change memory (iPCM), is characterized by significantly faster switching, lower energy consumption, and better endurance. The switching mechanism in iPCM, where both the SET and RESET states are crystalline, is still contentious. Here, using the ab initio density functional theory simulations, a conceptually new switching mechanism for iPCM is derived, which is based on the change in the potential landscape of the bandgap, associated with local deviations from the pseudobinary stoichiometry across the van der Waals gaps and the associated shift of the Fermi level. The crucial role in this process belongs to Ge/Sb intermixing on the cation planes of iPCM. These findings offer a comprehensive understanding of the switching mechanisms in iPCM and are an essential step forward to the insightful development of phase-change memory technology.</jats:p>