Various morphologies of polythiophene have been designed and successfully prepared by chemical oxidative polymerization in the presence of phase transfer catalyst (PTC) cetyltrimethylammonium bromide (CTAB) in aqueous medium. The morphologies of polythiophene could be controlled in ribbons, fibers and spherical particles by changing the concentrations of reductant, oxidant and phase transfer catalyst. The structure, thermal stability and the conductivity have been characterized, and a mechanism for the transformation of the morphology of polythiophene has been proposed. Various morphologies of polythiophene have been designed and successfully prepared by chemical oxidative polymerization in the presence of phase transfer catalyst (PTC) cetyltrimethylammonium bromide (CTAB) in aqueous medium. The morphologies of polythiophene could be controlled in ribbons, fibers and spherical particles by changing the concentrations of reductant, oxidant and phase transfer catalyst. The structure, thermal stability and the conductivity have been characterized, and a mechanism for the transformation of the morphology of polythiophene has been proposed.