Layered niobates and titanoniobates have been found to be strong solid-acid catalysts and have high surface areas while maintaining their crystalline structure. These materials can serve as models for the bond perturbations that affect the surface of solid acid niobates, which may have amorphous structures and thus not be amenable to characterization by x-ray diffraction. To understand the relationship between metal environment and surface properties, ⁹³Nb solid state NMR has been used to measure the electric field gradient and chemical shift anisotropy for layered niobates and their acid exchange forms. As ⁹³Nb is a quadrupolar nucleus, both the electric field gradient (EFG) and chemical shift anisotropy (CSA) for a given site can give information about the symmetry of the local structure and relate its influence on the acid site. Through a variety of solid-state NMR methods at multiple magnetic fields, changes in the niobium local structure in Dion-Jacobson type layered perovskites upon acid exchange have been observed even for metal sites not in immediate proximity to the hydroxyl group. Using similar methods, the types of local niobium environments in mesoporous niobium oxides have been characterized. The local niobium sites related to hydroxyl sites located in these porous materials have been distinguished from the bulk through correlation experiments.