AbstractBACKGROUND: Microsphere and/or hollow sphere formation of methyl‐substituted polyaniline derivatives was investigated via chemical polymerization where different sets of conditions were examined. It was found that a variety of parameters (e.g. types and concentrations of monomer and oxidant, polymerization time, solvent with and without acid) have a crucial influence on the morphology of the resulting polyaniline derivatives.RESULTS: Structures with desired morphologies (with or without microspheres and hollow spheres) may be obtained in a controlled manner by changing the parameters. Moreover, the electrochemical and optical properties of the polymers in the presence of acid and/or base were investigated via cyclic voltammetry and UV‐visible and electron spin resonance spectroscopic techniques. It is noteworthy that the morphologies of microspheres and/or hollow spheres remained unchanged after repeated acid and base treatments.CONCLUSION: Micro/hollow spherical structures were successfully prepared via chemical polymerization of various substituted anilines by using ammonium persulfate as oxidant. It was found that the type of oxidant and monomers along with the polymerization time are quite important factors for the formation of micro/hollow spheres. Furthermore, hydrogen bond formation does not play any crucial role for the formation of these spheres. Chemically and electrochemically doped/dedoped states of microspheres and/or hollow spheres are very sensitive, and give rapid response towards vapours of HCl and NH3, which makes them amenable for use in sensors. Copyright © 2009 Society of Chemical Industry