Highly porous polypyrrole (PPy)-coated TiO2/ZnO nanofibrous mat has been successfully synthesized. The core TiO2/ZnO nanofibers have an average diameter of ca. 100 nm and the shell of ultrathin PPy layer has a thickness of ca. 7 run. The NH3 gas sensor using the as-prepared material exhibited a fast response over a wide dynamic range and high sensitivity with a detection limit of 60 ppb (S/N= 3). Compared to conventional pristine PPy film, the improved performance in NH3 detection can be attributed to the free access of NH3 to PPy and a minimized gas diffusion resistance through the ultrathin PPy layer.