Chemical demulsification is the most widely used method for breaking water-in-diluted bitumen emulsions in oil sands processing. In this paper, the properties and the performance of six intermediates and three blends were investigated. The intermediates and blends were characterized by their relative solubility number (RSN). The results showed that the RSN is an additive property. The dehydration efficiency of the blends was higher than the individual components at the same dosage, indicating there were synergistic interactions among the components on blending. The performance of the demulsifiers was correlated to the interfacial tension (IFT), yield stress of underflow, and bitumen loss to tailings. The equilibrium IFT results did not illustrate any correlation with the performance of the demulsifiers. The yield stress of the underflow, which included settled solids, water, and a rag layer increased with increasing dosage of either intermediate or blend. In addition, the bitumen loss to underflow increased with increasing dosage of either intermediate or blend. The yield stress and bitumen loss to underflow reduced on blending the intermediates. The bitumen loss to underflow increased the size of the aggregates present in the underflow, increasing their immobility and constriction to flow, and eventually a higher yield stress.