A general route, involving swelling-evaporation processes, is proposed for the generation of polymer hollow nanospheres derived from polymer nanoparticles for the first time. Different swelling reagents, such as ethanol, o-toluidine, toluene, and carbon tetrachloride, have been used to study their effect on the morphology of the resultant polymer hollow structures. The evaporation conditions, such as the temperature and pressure, can be used to tune the size and shell thickness of the polymer hollow structures. The chemical structures of the polymer have been characterized with X-ray diffraction, Fourier transform infrared, and ultraviolet-visible spectroscopy. (c) 2007 Wiley Periodicals, Inc.