Microstructures of poly(N-methylpyrrole) have been generated by direct electrochemical oxidation ofN-methylpyrrole with poly(styrenesulfonic acid) in aqueous solution, using a micelle formation mechanism with gas bubble templates. These microstructures present a “doughnut”-like morphology with diameters ranging from 20 to 100μm. Other anionic surfactants, such as camphorsulfonic acid andβ-naphthalenesulfonic acid, have been also employed, results evidencing that the morphology of the microstructures depends on the nature of the surfactant electrolytes. The dimensions, abundance and texture of the microstructures have been modulated by varying the surfactant molecules, the electrochemical technique, and the distance between the working and counter-electrode. The generated microstructures have been characterized using electrochemical techniques, Raman and infrared spectroscopies, scanning electron microscopy and atomic force microscopy. Hollow microstructures-containing films madeof poly(N-ethylpyrrole)/poly(styrenesulfonic acid), which present remarkable electroactivity and electrostability,has been proved to interact with morphine molecules. Thus, systems based on this prominent material show a high ability to capture the drug molecules and to retain them for a long period of time.