In this work, the deposition of polypyrrole thin films on nanostructured surfaces is reported. It has been demonstrated that the deposition and growth of polypyrrole is enhanced by the formation of a pyrrole-terminated self-assembled monolayer on a gold surface. Surface nanostructuration has been achieved by the self-assembling technique and the deposition of the organic polymer by plasma-enhanced chemical vapor deposition (PECVD) method. The effect of several ω-(o-(pyrrolyl)alkanethiol on the SAM formation, as well as the polymerization time to control the nucleation process have been studied. Thin films compositions have been characterized by AFM and XPS techniques. Conductive measurements of the samples were performed using the four point probe method. A figure is presented.