Abstract: Thermal recovery techniques for producing oil sands have substantial environmental impacts. Surfactants can efficiently improve thermal bitumen recovery and reduce the required amount of steam. Such a technique requires solid knowledge about the interaction mechanism between surfactants, bitumen, water, and rock at the nanoscale level. In particular, oil sands ores have extremely complex mineralogy as they contain many clay minerals (montmorillonite, illite, kaolinite). In this study, molecular dynamics simulation is carried out to elucidate the unclear mechanisms of clay minerals contributing to the bitumen recovery under a steam–anionic surfactant co-injection process. We found that the clay content significantly influenced an oil detachment process from hydrophobic quartz surfaces. Results reveal that the presence of montmorillonite, illite, and the siloxane surface of kaolinite in nanopores can enhance the oil detachment process from the hydrophobic surfaces because surfactant molecules have a stronger tendency to interact with bitumen and quartz. Conversely, the gibbsite surfaces of kaolinite curb the oil detachment process. Through interaction energy analysis, the siloxane surfaces of kaolinite result in the most straightforward oil detachment process. In addition, we found that the clay type presented in nanopores affected the wettability of the quartz surfaces. The quartz surfaces associated with the gibbsite surfaces of kaolinite show the strongest hydrophilicity. By comparing previous experimental findings with the results of molecular dynamics (MD) simulations, we observed consistent wetting characteristics. This alignment serves to validate the reliability of the simulation outcomes. The outcome of this paper makes up for the lack of knowledge of a surfactant-assisted bitumen recovery process and provides insights for further in-situ bitumen production engineering designs.