An exploratory investigation was conducted using the NMR technique CRAMPS (combined rotation and multiple-pulse spectroscopy) to provide information on the types of organic functionality via hydrogen types present on the surface of tar sand residues. These residues were obtained from (1) solvent extraction using solvents of different polarity, and (2) isothermal pyrolysis at four different temperatures. The solvents hexane, toluene, and methylene chloride were used to extract the bitumen from a native tar sands. From carbon and hydrogen analysis, all three solvents removed essentially all of the bitumen from the mineral matrix. However, solid-state 1H NMR and diffuse reflectance infrared spectra show the presence of a small amount of organic material still in contact with the mineral matrix. After extraction with methylene chloride, the most polar solvent, tar sand residues contain less organic material than the tar sand residues obtained after solvent extraction with hexane, the least polar of the solvents. The hydrogen spectra of the tar sand residues show a greater amount of aromatic hydrogens than aliphatic hydrogens presumably because of heteroaromatics, which would be expected to associate more strongly with the mineral matrix. The 1H CRAMPS spectra of the tar sand residues obtained from the isothermal pyrolysis of the native tar sand show that a relatively large amount of unpyrolysized bitumen still remains with the mineral matrix even at a temperature of 380°C. For above 400°C, the 1 H spectrum changed dramatically, but the spectrum of the pyrolyzate tar sand residue still did not have the chemical shift resolution that was apparent in the spectra of the tar sand residues from solvent extraction. The major change in the 1H spectrum of the tar sand residue after pyrolysis above 400°C was the loss of paraffinic hydrogens as expected.