It was previously demonstrated that the use of a pyrrole-based silane (PySi) for surface treatment of Al alloys provides both active and barrier protection due to the deposition of a hybrid coating, containing polypyrrole and polysiloxane chains. To further explore these features, a wider range of Al substrates and different silane-based formulations in terms of silane molecule, solvent nature, water amount and pH, were investigated. Also, some tests were carried out by using aniline-based silane (AniSi). Structural/morphological characterization of the coatings, as well as the investigation of PySi solutions by diverse spectroscopic techniques, in addition to corrosion tests in NaCl, strongly support the very promising protection performance of the hybrid film. This is indicated as well from the preliminary results obtained with the AniSi-based approach. Thus, typical silane-based treatments with principally barrier action can gain in active properties if the silane compound contains monomers of conducting polymers as a funtional group.