The ellipsometric investigations of adsorption combined with corrosion and electrochemical measurements allow one to understand some regularities of iron (steel) passivation in neutral aqueous solutions by various organic inhibitors of metal corrosion (IMCs). The increase in the efficiency of the adsorptive passivation is demonstrated based on the example of using more hydrophobic substituted sodium phenylanthranilate (SPA); more importantly, the compositions on their basis are more effective IMCs than substituted SPAs themselves. This is often connected with ability of one of the components to initiate the adsorption of the other. This is why we investigate the design of the adsorption films during the sequential adsorption of the blend components. It was shown that, for many IMCs, the preliminary chemisorption of some IMC can stimulate an increase in ΔGA0. The passivating treatment of the metal surface via the layer-by-layer method can provide the best protection of metals from atmospheric corrosion. Progress in the development of the nontoxic compositions to produce conversion coatings and their passivation, as well as the protection of metals by volatile IMC, is considered.