The self-assembly of thiophene monomers and the subsequent oxidative polymerization of them has been studied using the vapour phase polymerization (VPP) platform. A variety of nano-structures were obtained by varying the polymerization conditions with regard to temperature, time, addition of a secondary oxidant and crystal formation in the oxidant layer. The electrochemical and physical characterizations of these nano-structured polythiophene materials were performed using cyclic voltammetry, electron microscopy, UV-vis spectroscopy, conductivity, contact angle and BET surface area measurements. The presence of nano-structures indeed enhances the redox capacity and increases the active surface area compared to the analogue film without nanostructures. The hydrophobicity of the polymeric film is also tuneable from different nano-structures forming on top of the film. Crown Copyright (C) 2014 Published by Elsevier B.V. All rights reserved.