Polypyrrole-coated SnO2 hollow spheres hybrid materials have been synthesized through an in situ polymerization of pyrrole monomers in the presence of preprepared SnO2 hollow spheres. The hybrids were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared spectrometer (FTIR), and thermogravimetric analysis (TG). Experimental data showed certain synergetic interaction existed in the hybrids, probably resulting in the enhanced thermal stability of polypyrrole coatings. Gas sensing tests showed that the hybrids possessed very fast response and high sensitivity to ammonia gas at room temperature, implying its potential application for gas sensors.