A novel double-shelled hollow (DSH) structure of ZnTiO3 microrods was prepared by self-templating route with the assistance of poly(diallyldimethylammonium chloride) (PDDA) in an ethylene glycol (EG) solution, which was followed by calcining. Moreover, the NH3 gas-sensing properties of the DSH ZnTiO3 microrods were studied at room temperature. The morphology and composition of DSH ZnTiO3 microrods films were analyzed using scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffractometry (XRD). The formation process of double-shelled hollow microrods was discussed in detail. The comparative gas-sensing results revealed that the DSH ZnTiO3 microrods had a higher response to NH3 gas at room temperature than those of the TiO2 solid microrods and DSH ZnTiO3 microrods did in the dark. More importantly, the DSH ZnTiO3 microrods exhibited a strong response to low concentrations of NH3 gas at room temperature.