High-resolution solid-state NMR techniques were used to investigate the surface structure of Cab-O-Sil fumed silica. H-1 NMR results obtained from CRAMPS, MAS-only and relaxation studies reveal the existence of both hydrogen-bonded silanols and isolated silanols on the Cab-O-Sil surface. A systematic dehydration study of fumed silica was carried out, with results on the quantity of each type of silanol on the surface at various dehydration stages. Si-29 CP-MAS experiments, including CP spin dynamics studies and various other relaxation studies, were employed to probe hydrogen bonding and the local structural environments of various hydroxyl groups of silica surfaces. Si-29 CP-MAS experiments on water-treated and deuterium-exchanged Cab-O-Sil indicate the existence of interparticle silanols and internal silanols in filmed silica. H-1 and Si-29 NMR show that for fumed silica both isolated and hydrogen-bonded silanols are present on the surface of an untreated sample, in contrast to the case of silica gel, where all silanols of an untreated sample are hydrogen bonded.