In the present study, selectively deuterated alkylamine ligands were prepared and subsequently used to modify the surface of porous silica. The resulting material was then reacted with either hexanoyl chloride or heptanoyl chloride to produce the corresponding alkylamide-modified surfaces. The wide-line H-2 NMR spectra of the intermediate and final materials were measured in the dry state and in the presence of both protic and aprotic solvents. The shapes of the resulting resonances are complex and are made up of spectrally broad and narrow components with widths in the restricted motion range (i.e., about 40 kHz) and widths characteristic of more motionally dynamic species. The relative contribution of the broad component is dominant in the dry state and in aprotic solvent spectra and is significantly decreased or absent in the spectra collected in polar solvents. These results can be explained via changes in the degree of interfacial hydrogen bonding between the amine and amide groups in the attached ligands and residual surface silanols.