Isotopic enrichment of Si-29 and DNP-enhanced NMR spectroscopy are combined to determine the detailed surface structure of a silicated alumina catalyst. The significant sensitivity enhancement provided by DNP is vital to the acquisition of multinuclear and multidimensional experiments that provide information on the atomic level structure of the species present at the surface. Isotopic enrichment not only facilitates spectral acquisition, particularly given the low (1.5 wt %) Si loading, but also enables spectra with higher resolution than those acquired using DNP to be obtained. The unexpected similarity of conventional, CP, and DNP NMR spectra is attributed to the presence of adventitious surface water that forms a sufficiently dense H-1 network at the silica surface so as to mediate efficient polarization transfer to all Si species regardless of their chemical nature. Spectra reveal the presence of Si-O-Si linkages at the surface (identified as Q(4)(3Al) Q(4)(3Al)) and confirm that the anchoring of the surface overlayer with the alumina occurs through Ally and Al-V species only. This suggests the presence of Q(3)/Q(4) Si at the surface affects the neighboring Al species, modifying the surface structure and making it less likely Al-VI environments are in close spatial proximity. In contrast, Q(1)Q(2) species, bonded to the surface by fewer covalent bonds, have less of an effect on the surface, and more Al-VI species are consequently found nearby. The combination of isotropic enrichment and DNP provides a definitive and fully quantitative description of the Si-modified alumina surface, and we demonstrate that almost one-third of the silicon at the surface is connected to another Si species, even at the low level of coverage used, lowering the propensity for the formation of Bronsted acid sites. This suggests that a variation in the synthetic procedure might be required to obtain a more even coverage for optimum performance. The work here will allow for more rigorous future investigations of structure-function relationships in these complex materials.