The paper presents the results of the electrochemical and surface study concerning the binder influence on protective properties of paint coatings. The protective films realized with various binders were applied on carbon steel substrate. The experiments carried out in a 3% NaCl solution, normal aerated at the room temperature. The experimental results show that the paint films containing binders with three-dimensional (3D) structure provide good protective properties. The best performance is exhibited by the paint films with the alkyd binder, due to their 3D structure formed as a result of chemical reactions of the binder with the oxygen from atmosphere during the curing process.