The molecular level characterization of heterogeneous catalysts is challenging due to the low concentration of surface sites and the lack of techniques that can selectively probe the surface of a heterogeneous material. Here, we report the joint application of room temperature proton-detected NMR spectroscopy under fast magic angle spinning (MAS) and dynamic nuclear polarization surface enhanced NMR spectroscopy (DNP-SENS), to obtain the Pt-195 solid-state NMR spectra of a prototypical example of highly dispersed Pt sites (single site or single atom), here prepared via surface organometallic chemistry, by grafting [(COD)Pt(OSi(OtBu)(3))(2)] (1, COD = 1,5-cyclooctadiene) on partially dehydroxylated silica (1psi02). Compound 1@SiO2 has a Pt loading of 3.7 wt %, a surface area of 200 m(2)/g, and a surface Pt density of around 0.6 Pt site/nm(2). Fast MAS H-1{Pt-195} dipolar-HMQC and S-REDOR experiments were implemented on both the molecular precursor 1 and on the surface complex 1@SiO2, providing access to Pt-195 isotropic shifts and Pt-H distances, respectively. For 1@SiO2, the measured isotropic shift and width of the shift distribution constrain fits of the static wide-line DNP-enhanced Pt-195 spectrum, allowing the Pt-195 chemical shift tensor parameters to be determined. Overall the NMR data provide evidence for a well-defined, single-site structure of the isolated Pt sites.