In this paper, we report a one-step method to obtain conductive polypyrrole thin films on flexible substrates. To do this, substrates were modified through allylamine plasma grafting to create a high amount of reactive amine groups on PDMS surface. These groups are used during polypyrrole particle synthesis as anchoring points to immobilize the polymeric chains on the substrate during polymerization. Surface morphology of polypyrrole thin films are modified, tailoring the polyelectrolyte used in the polypyrrole synthesis obtaining different shapes of nanoparticles that conform to the film. Depending on the polyelectrolyte molecular weight, the shape of polypyrrole particles go from globular (500 nm diameter) to a more constructed and elongated shape. The films obtained with this methodology reflected great stability under simple bending as well as good conductivity values (between 2.2 ± 0.7 S/m to 5.6 ± 0.2 S/cm).