Master alloys containing Zirconium (Zr) serve as effective grain refiners in most commercial cast magnesium (Mg) alloys. However, their efficacy is diminished in Mg–Al series alloys due to the formation of Al–Zr compounds. In this work, a novel Mg-GNP@MgO master alloy was prepared utilizing the in-situ reaction between CO2 and Mg. The grain refinement efficiency of this composite inoculation on Mg–9Al alloys was systematically investigated using SEM-EBSD, HRTEM observations, Density Functional Theory (DFT), and Sharp Interface Model (SIM) calculations. The findings suggest that the composite grain refiner (GNP@MgO) exerted a notable refining influence on Mg–9Al alloy. Through the conventional casting process, the average grain size was refined to approximately 13 μm upon the addition of 3 vol% GNP@MgO, achieving a grain refinement efficiency of 90 %. The enhanced refining efficiency arises from the synergistic control over the nucleation and growth processes of α-Mg grains, facilitated by GNP@MgO particles. This process includes improved heterogeneous nucleation, triggered by the newly formed Al4C3 phases through the interaction between GNPs and Al element, followed by the limited expansion of α-Mg grains induced by the nano-sized MgO particles. The MgO particles predominantly gather around grain boundaries to establish stable nano-coating layers, thereby exerting a substantial Zener pinning effect. The pinning role played by the MgO nanoparticles was also verified by a sharp interface model. The findings in this work not only carve out a new avenue for the grain refinement of cast Mg–Al alloys but also inspire fresh perspectives for the development of novel grain refiners.