The use of nuclear magnetic resonance (NMR) spectroscopy for characterising microencapsulated tuna oil powders (25% and 50% w/w oil) and assessing the behaviour of the microcapsules on their exposure to water, simulated gastric fluid or to sequential exposure of simulated gastric and intestinal fluids was examined. The matrices used for encapsulation were physical mixtures of casein or whey protein in combination with carbohydrates (dextrose monohydrate with either dried glucose syrup or a physically modified resistant starch) or heated mixtures of these matrices. Solid-state 13 C cross-polarised magic angle spinning NMR and dipolar de-coupled magic angle spinning NMR record the 13 C NMR signals of the encapsulant material and that of the encapsulated oil, respectively. 1 H and 13 C solution NMR were used to investigate the relative increase in mobility of the various encapsulant matrices due to their dissolution on exposure to gastrointestinal fluids. The results suggested that the dissolution characteristics of matrices of microencapsulated oil powders were dependent on the type of milk protein and carbohydrate used and whether the protein-carbohydrate matrices were heat-treated prior to encapsulation of the oil.