Clays cause problems in all crucial stages of bitumen extraction, and they affect bitumen recovery and waste management. It is thus of great importance to understand the mineralogy, chemistry, and surface properties of clays to improve both bitumen recovery and tailings treatment. Four petrologically different types of Alberta oil sands ores-called "end-members"-were examined in this study by cation exchange capacity (CEC), specific surface area (SSA), total specific surface area (TSSA), and negative layer charge density (LCD) measurements in order to better understand the effects of clay surface properties on bitumen nonaqueous extraction and solvent recovery from the extraction tailings. The surface properties are primarily controlled by the mineralogy of the petrologic end-members, mainly by the type and quantity of clay minerals. CEC, SSA, TSSA, and LCD increased as the amount of 2:1 clays (illite and illite-smectite), in particular expandable interstratified illite-smectite, increased. CEC values increased with increasing SSA and TSSA. The number of H-aggregates increased and the number of monomers decreased in the second derivative spectra of Rhodamine 6G and Methylene Blue as the 2:1 clays content in the petrologic end-members increased. This indicated a greater negative layer charge density with an increasing amount of 2:1 clays. The molecular aggregation of the organic dyes (Rhodamine 6G and Methylene Blue) was observed in the second derivative spectra for petrologic end-members bearing >25 wt % of 2:1 clays. Overall, the results indicate that interstratified illite-smectite may be largely responsible for high CEC, SSA, TSSA, and LCD in the fine size fractions of petrologic end-members from Alberta oil sands.