Silica microspheres encapsulating ibuprofen in separated domains at the nanometre scale are formed by spray-drying and sol-gel processes. A detailed (1)H and (13)C NMR study of these microspheres shows that ibuprofen molecules are mobile and are interacting through hydrogen bonds with other ibuprofen molecules. (1)H magnetisation exchange NMR experiments were employed to characterize the size of the ibuprofen domains at the nanometre scale. These domains are solely formed by ibuprofen, and their diameters are estimated to be ∼40 nm in agreement with TEM observations. The nature and formation of these particular texture and drug dispersion are discussed.