An alternative approach was developed for the surface treatment of as-received commercial aluminium alloys 6082-T6, 5083-H111 and 2024-T3 by using a pyrrole-based silane. One immersion step is sufficient for poly(pyrrole-siloxane) film deposition, with good adhesion and desirable morphological features. The combination in a single coating of polysiloxane linkages, acting as a barrier for aggressive species penetration towards the metal surface, and polypyrrole units manifesting active anodic protection, together with high degree of compactness, explains the significantly improved corrosion protection of the composite film in comparison to simple coatings of polymethylsiloxane and polypyrrole.