Electrochemical techniques (potentiodynamic polarization curves and electrochemical impedance spectroscoy (EIS) were used to study the effect of dibenzylsulfoxide adsorption on the dissolution of iron in 5% hydrochloric acid. To discuss different proposed mechanisms of dibenzylsulfoxide adsorption at the iron surface a quantum chemical topological method was used, which is suitable for studying the interaction of organic molecules with metal surfaces. Based on the results of the topological modeling, adsorption followed by reduction of dibenzylsulfoxide to sulfide is most favorable. EIS shows the possible effect dibenzylsulfoxide has on the electrochemical desorption of adsorbed hydrogen. Topological studies indicate strengthening of the bond of the adsorbed hydrogen to the metal due to adsorption of the inhibitor.