Surface initiated radical polymerization (SIRP) is an elegant and efficient method to produce polymer chains attached to surfaces with a high graft density. Growth of polymer chains from a gold surface requires the formation of a self-assembled monolayer (SAM) of thiols functionalized by reactive groups (alcohol or carboxylic acid) in order to covalently bind free radical initiator species. However, thiol desorption induced by the temperature imposed for polymerization impedes the growth of polymer chains,. We propose therefore to coat a gold electrode with a polypyrrole (PPy) derivative containing carboxylic acid pendant groups. The resulting conducting polymer layer was shown to be strongly attached to the surface. Grafting of the initiator (azo compound) and SIRP of styrene were successfully performed on this organic layer, as demonstrated by X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (TOF SIMS), and contact angle measurements. The roughness, the morphology, and the surface uniformity of the films were investigated by atomic force microscopy (AFM). Finally, cyclic voltammetry experiment,,; were carried out to study the influence of the polystyrene layer on the electrochemical behavior of the conducting polymer.