The development of conducting polymers has become the aim of many research groups. This paper describes attempts to carry out a plasma polymerization of polypyrrole (PPy) on a nanostructured surface by attaching a 11-(pyrrol-1-yl-undecyl)dimethylchlorosilane molecule onto a silicon wafer surface in order to form a self-assembled monolayer (SAM). The effect of theSAMin the polymerization process is also studied. Important differences in the polymer deposition are found whether or not the surface has been modified with a SAM. Atomic force microscopy (AFM) and time-of-flight secondary ion mass spectrometry (TOFSIMS) analyses are performed to study the morphology, deposition, and growth of polypyrrole.