Surface-enhanced Raman scattering (SERS) is a process with origins, electromagnetic and chemical. The electromagnetic enhancement consists of the excitation of surface plasmons in the metallic support of the thin film. With only the electromagnetic enhancement mechanism, the surface spectra should not differ from volume Raman spectra. However, between SERS and volume Raman spectra, there are differences resulting from the chemical reactions taking place at the polymer/metal interface, intermediated by solvent molecules, that finally depend on the types of polymers and metallic supports. Polyaniline (PAN) is an excellent material to emphasize the chemical component of SERS. This is due to its particular structure with a repeating unit that contains two entities at different weights-a reduced state and an oxidized state-that, in turn, react differently with a metallic substrate. SERS spectra depend on the oxidizing properties of the metal surface, which involves an intermediate compound of the types Ag2O and Au2O3 when N-methyl-2-pyrrolidinone is used as the solvent. This article presents new results concerning the surface chemical effects that produce variations of the PAN SERS spectra. The SERS spectra of the PAN emeraldine base (PAN-EB) layered on Au support are characterized by a semiquinoid structure that we believe is induced on the intermediate compound Au2O3. In the presence of H2SO4, the SERS spectra change gradually as the degree of acid protonation doping increases. The SERS spectra of the fully protonated PAN-EB are identical to those obtained on PAN emeraldine salt (PAN-ES) synthesized by cyclic voltammetry in an acid medium and are invariable with the type of metallic support. The SERS spectra show that the emeraldine salt can be partially or totally deprotonated with water or NH4OH. The deprotonation is complete for the Ag support and partial for the Au support. The SERS spectra of the fully protonated PAN-EB are characterized by a double band with maxima at about 1330 and 1370 cm(-1). Although the generation process of positive charge on the macromolecular chain of PAN-EB doped in the presence of (C4H9)(4)NBF4 is similar to that due to protonic acid doping, involving cation addition (C4H9+ or H+ ions, respectively) in SERS spectra, the complex band situated at about 1330-1370 cm(-1) no longer appears. The doping of PAN-EB with FeCl3 produces two polymer cm forms: a salt type characterized by a protonated structure similar to that found for PAN-ES and a base type similar to the leucoemeraldine form.