Abstract Solvent extracts of Athabasca tar sand were analyzed by the Brown-Ladner method, the Takeya et al. method, and the Speight method on the basis of the 1H-NMR data and by 13C-NMR spectroscopy. The structural characteristics of Athabasca tar sand derivatives were also compared with those of coal-hydrogenolysis products. The results show that the structural characteristics of hexane solubles, monomers consisting of one aromatic ring substituted highly with C6 aliphatic chains, resemble those of the oil fraction produced during the initial stage of the hydrogenolysis of Taiheiyo coal. However, the structural characteristics of the hexane insoluble-benzene solubles, oligomers consisting of 2 aromatic rings substituted highly with C4–5 aliphatic chains, are different from those of any coal-hydrogenolysis products. In addition, the close agreement between the fa value obtained by the Brown-Ladner method and 13C-NMR may indicate that, for solvent extracts of Athabasca tar sand, the assumption in the Brown-Ladner method that the atomic H/C ratio of aliphatic structures is 2 is proper.