Hollow microspheres with porous shells of poly(o-toluidine) (POT) and poly(o-methoxyaniline) (POMA) have been prepared via chemical polymerization on glass substrate using alkali-guided method. It is found that the microspheres with an average diameter of 5.0 mu m are deposited on the top of the monolayer of small nanospheres. The effects of the preparation conditions such as monomer concentrations and the pH values of the reaction solutions on the morphology the spheres deposited on the substrate are investigated. The products are characterized by SEM, TEM, FT-IR, and UV-vis measurements. Moreover, the formation mechanism of this porous structure is also proposed. (c) 2009 Elsevier B.V. All rights reserved.