The HF . BF3 superacid-catalyzed hydrocracking of tar sands bitumens and asphaltenes leads to deep-rooted chemical changes which affect both the aliphatic and aromatic constituents of the feedstocks even under mild experimental conditions, resulting in high yields of volatiles and liquid products. In contrast to conventional catalytic hydrocracking following free-radical mechanisms, the superacid-catalyzed reaction follows ionic mechanisms, yielding products very different from those following the free-radical reactions. When methylcyclohexane (MCH) is employed as a hydrogen-donor solvent, new products resulting from the oligomerization of MCH appear. MCH neat, without bitumen or asphaltene, does not oligomerize under identical conditions. These preliminary results point to the commercial potential of using the volatile HF . BF3 superacid in the upgrading of bitumen and the oligomerization of cycloalkanes.