In this contribution we report on the oxidative dehydrogenation (ODH) activity of silica-supported boron oxide prepared via incipient wetness impregnation. Characterization of pristine and spent catalysts with infrared, Raman, and solid-state NMR spectroscopy reveals the presence of both isolated and aggregated oxidized boron sites. The results of these investigations, in combination with our earlier work on bulk boron-containing ODH catalysts (e.g., h-BN, metal borides, and elemental boron), bolster the hypothesis that oxidized boron species in situ formed on the surface of these materials are responsible for the exceptional catalytic behavior. We anticipate that investigation of supported boron materials can provide insight into the structural characteristics required for selective boron-containing ODH catalysts.