The hollow Au nanospheres were successfully prepared by the template method. The poly(styrene-co-2-aminoethyl methacrylate hydrochloride) (P(St-co-AEMH)) nanoparticles synthesized by the emulsion polymerization were used as the templates. After coating by Au colloidal nanoparticles and the formation of Au shells, the interior templates were etched out by sulfuric acid, leading to the formation of Au hollow nanospheres. The structure and morphology of the nanoparticles and hollow nanospheres were carefully investigated by the fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray analysis (EDX), wide-angle X-ray diffractometer (WAXD), and thermal gravimetric analysis (TGA) techniques.