The use of surface enhanced Raman scattering (SERS) effect as a technical tool for the characterization of passive films formed on different substrates as copper, CuZn alloys and iron electrodes is reviewed. Passive films formed on copper and its alloys in the presence of benzotriazole (BTAH) have been characterized as being composed of different types of surface complexes, [Cu(I)BTA]_n and [Cu(I)ClBTAH]₄, depending whether chloride ions are absent or present in the electrolyte solutions. The SERS effect of passive films formed on iron in different electrolytes has been obtained by the electrochemical deposition of silver over the passive film or by the deposition of silver over iron prior to the generation of the passive film. The SERS results support the assignment of the passive film to a film of Fe(OH)₂ separating the metal and another film of δ-FeOOH. It has also been shown that other iron species can be formed depending on the electrolyte composition.