The 31 P directly excited MAS NMR spectra of the (ZIF-8)0.3/(IG)0.7 physical mixture, [(ZIF-8)0.3(IG)0.7] composite and 50(Na2O)-50(P2O5) recorded under quantitative conditions (Fig. and Fig. for a direct comparison) had a dominant signal at -20 ppm. This signal is typical of Q 2 metaphosphate tetrahedral units and minor signals around -10 (Q 1 ) and 0 ppm (Q 0 ) that are ascribed to a very small degree of depolymerisation or the slight off-stoichiometry of the 50:50 Na2O:P2O5 ratio (Table ). Upon composite formation of [(ZIF-8)0.3(IG)0.7], these two Q 1 and Q 0 signals appear more intense than in the (ZIF-8)0.3/(IG)0.7 physical mixture and the inorganic glass, 50(Na2O)-50(P2O5) as shown in Fig. , potentially due to interactions as explored below. The Na MAS NMR spectra of all three materials (Fig. ) are virtually identical with an asymmetrically broaden resonance centred at about -15 ppm and a low-frequency tail capturing a continuous distribution of quadrupolar parameters as typically observed for structural disorder in glassy materials. These data further reinforce the structural integrity of the inorganic glass upon mixing and thermal treatment captured by PDFs. In order to probe spatial proximities, 1 H 31 P cross polarisation (CP) MAS NMR spectra of the (ZIF-8)0.3/(IG)0.7 physical mixture and the [(ZIF-8)0.3(IG)0.7] composite were recorded (Fig. and Fig. ). In this experiment, a transfer of polarisation occurs between the highly polarised spin (i.e., 1 H) to the weakly polarised spin ( 31 P) and establishes a heteronuclear dipolar contact that is related to their internuclear distance. CP spectrum is not a quantitative measurement of the site distributions. Strong 1 H 31 P CP MAS NMR signals for Q 0 , Q 1 and Q 2 signals are observed in both (ZIF-8)0.3/(IG)0.7 physical mixture (Fig. ) and [(ZIF-8)0.3(IG)0.7] composite (Fig. ) and are associated with polarisation transfer from the 1 H in the ZIF-8 to 31 P of the phosphorous tetrahedra in the inorganic glass. P CP signals are also observed in inorganic glass and result from the very weak 1 H signals (Fig. ) in this phase, which likely arises from POHlike moieties in Q n environments.