High resolution-magic angle spinning nuclear magnetic resonance (HR-MAS NMR) allows the application of solution-state NMR experiments to samples that are not fully soluble and contain solids. Only the species in contact with the solvent system employed become NMR observable. In this study utilizing D2O as the solvent system we show it is possible to examine the structures at the solid−aqueous interface of a whole soil. Combining one- and two-dimensional HR-MAS NMR allowed, for the first time, the identification of fatty acids, aliphatic esters, and ethers/alcohols as prominent species at the solid−aqueous interface of the soil with signals from sugars and amino acids also apparent. Few, if any signals from aromatic protons were observed when the soil was swollen in aqueous media, although these signals are observed in extracts from the same soil and when the soil is swollen with a more penetrating solvent (DMSO-d 6) which is known to disassociate hydrogen bonds. These findings indicate that the soil aromatic moieties are protected in hydrophobic regions which are not water accessible. Furthermore, when the soil was amended with a herbicide (trifluralin), direct observations of interactions between the protons on a xenobiotic and the surrounding soil matrix were possible for the first time. HR-MAS promises to be a method that can be widely applicable to a range of complex environmental samples without the need for extraction, pretreatment, or purification.