Supplementary materials are available online at https://www.sciencedirect.com/science/article/pii/S1359645423004780#sec0023 . Copyright © 2023 The Author(s). Interfacial segregation of selected elements can be exploited to manipulate the potency of solid substrates for heterogeneous nucleation, thus controlling the solidification process. As the native inclusions in Mg alloys, MgO acts as the nucleating substrate, but it has rarely been studied in terms of its interactions with alloying elements. In this work, investigations of yttrium (Y) segregation at interfaces between native MgO particles and Mg in an Mg-0.5Y alloy were carried out by state-of-the-art aberration-corrected scanning transmission electron microscopy (STEM) and associated spectroscopy. Experimental results show that native MgO particles in Mg-0.5Y possess two typical morphologies: truncated octahedron primarily faceted by {111}MgO and minorly by {100}MgO, and cubic shape with unique {100}MgO facets. Y atoms are found to segregate at both Mg/{111}MgO and Mg/{100}MgO interfaces, leading to the formation of two different 2-dimensional compounds (2DCs). The 2DC at the Mg/{111}MgO interface is identified as two atomic layers of a face-centered cubic Y2O3 phase in terms of crystal structure and chemistry, whilst it is an Mg(Y)-O monolayer at the Mg/{100}MgO interface, coherently matching with the terminating {100}MgO plane. Discussion is focused on the mechanisms underlying the formation of the 2DCs, their effects on the nucleation potency of MgO particles, and grain refinement. This work sheds light on how heterogeneous nucleation can be manipulated by altering the nucleation potency of a substrate through deliberately promoting elemental segregation of carefully chosen element(s). EPSRC under grant number EP/N007638/1. The SuperSTEM Laboratory is the U.K National Research Facility for Advanced Electron Microscopy, supported by EPSRC under grant number EP/W021080/1. SHW gratefully acknowledges the China Scholarship Council (CSC) for financial support.