We have reported recently a novel method for cross-linking conjugated polymers involving a “precursor polymer” route, where the electrochemical method can be used to prepare ultrathin films on conducting metal and metal oxide surfaces. In this paper, we present the design, synthesis, protocol, and recent results in the application of these thin film materials. An emphasis will be given on how these films are characterized in-situ by a combined surface plasmon spectroscopy (SPS) and electrochemical approach. As a methodology, the concept can be extended to new methods of electrodeposition, patterning, and grafting of conjugated polymers on electrochemically addressable metal surfaces. Compared to spin-cast or electropolymerized monomer films, they are very robust both thermally and mechanically. Other applications of these films to sensors, dielectric materials, non-lithographic patterning, etc. are currently being investigated.