Wettability alteration of carbonate reservoirs from oil-wet to water-wet is an important method to increase the efficiency of oil recovery. Interaction between surfactants and polymers can enhance the effectiveness of surfactants in EOR applications. In this study, the interaction of polyethylene glycol (PEG) with an ionic surfactant, sodium dodecyl sulphate (SDS), is evaluated on an oil-wet carbonate rock surface by using contact angle measurements. The results reveal that wettability alteration of carbonate rocks is achieved through PEG/SDS interaction on the rock surface above a critical aggregation concentration (CAC). The behaviour of PEG/SDS aqueous solutions is evaluated using surface and interfacial tension measurements. Furthermore, the effect of PEG and SDS concentrations and impact of electrolyte addition on PEG/SDS interaction are investigated. It is shown that electrolyte (NaCl) can effectively decrease the CAC values and accordingly initiate the wettability alteration of rocks. Moreover, in a constant SDS concentration, the addition of NaCl leads to a reduction in the contact angle, which can also be obtained by increasing the aging time, temperature and pre-adsorption of PEG on the rock surface.