The simple preparation of a novel family of smart polymers based on acid-base complexes between an acidic conjugated polymer (poly(2-(4-methyl-3-thienyloxy)ethanesulfonic acid)) and various amine-containing molecules is described. The neutralization of the acid form of the polymer can be monitored optically in real time through the decrease of the 800 nm absorption band, characteristic of a self-acid-doped state. Moreover, by electrostatically binding adequate responsive substituents, thermochromic, ionochromic, photochromic, and biochromic materials have been easily developed. These optical features seem related to a conformational change of the conjugated main chain driven by side-chain disordering. Furthermore, aminosilane-treated substrates can undergo further modification through electrostatic interactions with partially pre-neutralized polymers, yielding very efficient electrochemical solid-state sensors. It is believed that such a simple methodology, based on electroactive and photoactive supramolecular polymeric assemblies, may open the way to the design of integrated chemical systems incorporating both a trigger and a transducer and can find applications in the areas of biosensors, drug screening, and diagnostics.