Due to its extremely low natural abundance and quadrupolar nature, the O-17 nuclide is very rarely used for spectroscopic investigation of solids by NMR without isotope enrichment. Additionally, the applicability of dynamic nuclear polarization (DNP), which leads to O-17 sensitivity enhancements of 2 orders of magnitude, to 130 is wrought with challenges due to the lack of spin diffusion and low polarization transfer efficiency from H-1. Here, we demonstrate new DNP-based measurements that extend O-17 solid-state NMR beyond its current capabilities. The use of the PRESTO technique instead of conventional H-1-O-17 cross-polarization greatly improves the sensitivity and enables the facile measurement of undistorted line shapes and two-dimensional H-1-O-17 HETCOR NMR spectra as well as accurate internuclear distance measurements at natural abundance. This was applied for distinguishing hydrogen-bonded and lone O-17 sites on the surface of silica gel; the one-dimensional spectrum of which could not be used to extract such detail. Lastly, this greatly enhanced sensitivity has enabled, for the first time, the detection of surface hydroxyl sites on mesoporous silica at natural abundance, thereby extending the concept of DNP surface-enhanced NMR spectroscopy to the O-17 nuclide.