In this paper, we report several strategies for preparing smart coating based on the synthesis, electrodeposition, and patterning of ultrathin films of conjugated polymer network (CPN) films on flat electrode surfaces using the "precursor polymer" approach. This involves a rational synthesis and design of a precursor polymers followed by careful electrodeposition and characterization of ultrathin films and coatings on conducting substrates. A precursor design involves the tethering of electropolymerizable monomers to polymer backbones that can have "active" or "passive" electro-optical properties. This has resulted in the preparation of smooth, high optical quality films, which should be important for practical electro-optical coatings applications. Characterization of these films has been made using surface sensitive spectroscopic and microscopic analytical techniques. Copoly-merization with monomers, polymer backbone design, and grafting on modified surfaces are key points in a coatings strategy. Novel methods of in-situ characterization techniques have also been developed combing electrochemistry and surface plasmon resonance techniques. These coatings have found applications for devices as well as sensors.