Recent research has highlighted wettability alteration as the main consequence of the different mechanisms involved in technologies such as adjusted brine composition water flooding (ABCW) and low-salinity water flooding (LSW). However, studies are still needed to give a phenomenological explanation, and the most influential components of the system (rock–oil–brine) must be clarified. This work focuses on determining the most relevant variables for the smart water effects to occur. Static (contact angles) and dynamic tests (coreflooding) were conducted. For the static tests, aged Berea slices, a specific crude oil (27° API, 10.5 cp at 60 °C), and mono and divalent inorganic salts (Na+, K+, Ca2+, and Mg2+/Cl−) were used in 3 different concentrations of 1000, 3000, and 5000 ppm (ionic strength variation between 0.015 and 0.06) to establish the wettability state by measuring the contact angles of the system. When salts containing chloride were evaluated, a decrease in oil wettability was observed at 5000 ppm. At 3000 and 1000 ppm, tendencies depended on the particular cation. Three brines were selected from the contact angle experiments to be used in coreflooding assays, considering a particular design to identify ion exchange from the rock–oil–brine system. The first assay was carried out in the absence of crude oil as a baseline to determine the ion exchange between the brine and the rock, and a second test considered crude oil to provide insight into ion exchange and its effect on displacement efficiency. Capillary electrophoresis was used in this research as a novel contribution to the systematic study of oil displacement tests, and it has proven to be a powerful tool for understanding the mechanisms involved. The results show that the variations in the concentrations detected in the displacement effluents were the product of the interactions between rock, oil, and brine since the concentrations measured in the absence of oil phase were comparable to those in the injection brine. Significant variations in the effluent ion concentrations were determined for the different brines used, and increases in the pressure differentials were observed for the KCl and CaCl2 brines. These results suggest that the oil–brine ion exchange (salting in/out) represents a relevant mechanism to explain the observed displacement efficiencies and differential pressures. The ionic enrichment of the water phase due to the salting in/out effect needs to be better understood.