Coating strategies for corrosion protection based on intrinsically electronic conducting polymers, become an important research field mainly due to restrictions to the use of heavy metals, which are related to environmental problems. This work presents the corrosion protection behavior of different metals by using coatings based on acrylic blends formed by polyaniline and poly(methyl methacrylate). Raman spectroscopy revealed that the oxidation state of the PANI component of the blend at undamaged films, depends on the metal surface used as substrate. Results indicate that the degree of redox conversion of polyaniline, from emeraldine to leucoemeraldine state, strongly depends on the reducing power of metals showing a galvanic coupling between the substrate and polyaniline. On the other way, results reveal that PANI acts as an anion reservoir, which can release anions in a smart way when damage is produced on the surface of the coating forming a second physical barrier to avoid penetration of aggressive ions. This phenomenon was observed for all metal studied in this work.