The nature of the interface between the ZIF and the inorganic glass is best obtained from considering both the residues of the MLR analysis of the X-ray PDFs data (amongst other analysis methodologies) and multinuclear multidimensional NMR spectra capturing spatial proximities. This MLR approach might be more suitable for small data series with a small number of components, whereas PCA might be more suitable for analysing more complex composites. The contribution to the PDFs from interfacial correlations are, however, inevitably small and are at the limit of the accuracy of current experiments and also of the MAS NMR. Correlated 1 H 31 P NMR spectra between nuclear spins are uniquely present in each of the MOF-CIGC component and provide a powerful approach to probing neighbouring environments which are also postulated from other NMR data. The demonstration of a MOF IG interaction in our case predicts a better mechanical performance compared to ZIFs, often obtained as microcrystalline powders. Interaction between individual components in MOF-composite materials have been previously computationally predicted, through this work proves that the experimental elucidation of these interactions is also possible.