Polyacrylonitrile colloidal microspheres have been successfully prepared with different concentrations of electrospraying polyacrylonitrile solutions. The morphology of the colloidal spheres has two kinds of structures and is strongly affected by electrospray-ionization parameters, such as the polymer concentration, applied voltage, and distance between the electrodes. The solvent can also affect the morphology of polyacrylonitrile. The optimum conditions for preparing colloidal spheres have been found, and differential scanning calorimetry results indicate that polyacrylonitrile colloid spheres are amorphous. (c) 2006 Wiley Periodicals, Inc.