Chemical injection has proved to have superior performance in improving oil recovery. The injected chemicals are typically designed to participate in interfacial interactions at liquid–liquid and rock-liquid interfaces while having minimum adsorption onto the rock surface. This study endeavors to investigate the interfacial activity of several environmentally-friendly halogen-free ionic liquid-based catanionic surfactants synthesized via an ion exchange reaction between cationic imidazolium-based ionic liquids, [Cnmim][Cl] (n = 4,8,12), and anionic surfactants, sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, and dioctyl sodium sulfosuccinate. Results revealed that the catanionic surfactant synthesized with medium-chain ionic liquid (n = 8) and sodium dodecyl sulfate exhibited higher interfacial activity, demonstrating a minimum crude oil-brine interfacial tension of 0.17 mN/m and wettability alteration index of 0.79. The results of the adsorption study also revealed the adsorption density of 2.19 mg/g onto the dolomite surface for 2000 mg/L of catanionic surfactant in seawater, which was considerably lower than cetyltrimethylammonium bromide adsorption (11.55 mg/g) in the control experiment. Finally, the surface energy analysis of liquid-rock interactions was conducted using the concept of work of adhesion to scrutinize the wettability alteration and adsorption processes, where a direct relationship between work of adhesion and adsorption density was proposed. According to the results of this study, medium chain ionic liquid-based catanionic surfactant containing dodecyl sulfate anion, exhibiting excellent interfacial activity and low adsorption tendency onto the dolomite surface, could be considered in future chemical enhanced oil recovery applications.