Preparation of polymeric membranes based on polyethersulfone (PES) modified by adding different amounts of a pore-forming agent (PVP) is presented, and potential application of the membranes obtained for removal of phenol from the liquid phase is examined. The addition of various amounts of PVP has been shown to bring about changes in the content of the surface oxygen groups, but has no significant effect on the chemical character of the groups and acidic groups dominate. Filtration by phenol solution leads to significant changes in the total content of surface oxides; however, the acidic groups remain dominant. Membranes characterized by higher porosity exhibited more stable and higher rejection ratio for phenol removal. Although all the membranes were characterized by similar rejection ratios for phenol removal, the cake resistance (Rc) and pore resistance (Rp) values were found to depend significantly on the structure and porosity of the membrane applied for filtration.