The oil (diluted bitumen)–water separation efficiency at steam-assisted gravity drainage (SAGD) process conditions has been evaluated in a laboratory environment by using a custom-built batch gravity setup, using SAGD field fluids and commercial gas condensate as a diluent. The key parameters and conditions investigated are solvent amount, shear conditions, water-to-oil ratio, and the presence and wettability of fine solids. The results demonstrate the complexity of the oil–water separation process, affected by the dependence of the investigated parameters from one another. A new quantification approach is introduced to facilitate the oil–water separation efficiency evaluation, based on the proposed descriptor, referred to as a separation efficiency index (SEI). Defined as the average of the residual water-in-oil and oil-in-water indices, SEI ranges from 0 to 1, where 1 represents a “perfect” (complete) separation and 0 corresponds to a complete emulsification. The SEI allows one to describe the separation efficiency throughout the entire separation vessel volume, using discrete vertical water distribution profiles, and represents the separation efficiency with a single number, regardless of the experimental approach taken. The findings show that in the range of solvent concentrations of 30 vol % or lower, the mixing speed affects the separation performance and becomes predominant at the relatively low solvent concentrations of 10 and 20 vol %. The amount of solvent added becomes predominant in the oil–water separation process and overcomes all other effects in the highest solvent addition (40 and 50 vol %) range. The presence of water-wet solids improves the separation performance, while the presence of oil-wet solids impedes the oil–water separation. The results presented in this study, in particular the proposed SEI, are important for improving the oil–water separation efficiency and can be used to develop operational envelopes and new solvent injection strategies, in terms of location, amount, and stages, further improving the quality of the oil product obtained in SAGD.