Diverse coke deposition mechanisms and models, all supported by experimental data, have been proposed for catalytic hydrogenation processes related to heavy oil and bitumen refining. The influence of multiphase behavior on the observed deposition mode is an important but unresolved question in this literature. The model mixture Athabasca vacuum bottoms (ABVB) + decane, which is shown to exhibit L1L2V phase behavior at elevated temperatures and a commercial heavy oil hydrotreating catalyst (NiMo/gamma-Al2O3) were employed in this preliminary investigation. Under sedimentation conditions, the impact of phase behavior, per se, on the amount of coke deposited on and within catalyst pellets and the distribution of coke within catalyst pellets was found to be a secondary one despite the differences in the physical properties of the solvent-rich L1 phase and asphaltene-rich L2 phase. In all cases, the exterior surfaces of pellets were coated with a thick nanoporous coke layer. The ratio of pore surface area to pore volume also increased with the extent of reaction in all cases, indicating that larger pores are filled in part or plugged in preference to smaller ones. Observed differences in the properties of coked catalyst exposed to the L1 and L2 phases and to multiphase environments are attributed to differences in the asphaltene aggregate size distribution in the two phases and to multiphase hydrodynamic effects.