By combining the spectroscopic quality of a crystalline phase with the outstanding thermal and chemical stability of the matrix glass, nanocrystal‐in‐glass composites (NGCs) exhibit excellent optical properties. However, strong interfacial diffusion occurs during high‐temperature encapsulation, leading to the erosion of the nanocrystals and detrimental effects on the final performance. The control of interfacial diffusion has so far relied on intuition and experience, with the underlying physical mechanisms remaining largely unknown. In this study, through atomistic simulations and experimental verification, we have developed atomic models of NGCs, revealing the dynamic characteristics of the interface and elucidating how the glass structure can regulate the interface diffusion. Finally, we demonstrate how a tunable interface can be achieved through compositional adjustments of the glass matrix.