For grafting polypyrrole layers on oxidicsubstrates, the synthesis and characterization of a newadhesionpromoter 11‐(pyrrol‐3‐yl) undecyl trimethoxysilane (PyTMS) were described in this article. The oxidation potential of PyTMS was determined by cyclic voltammetry. The grafting behavior of such an adhesionpromoter on oxidized surface and chemical deposition of polypyrrole over the modified oxidized