Polyaniline (PANI) is a promising functional polymer in the field of toxic gas detection. In this paper, nano-branched coaxial PANI fibers were grown on electrospun poly(methyl methacrylate) (PMMA) nanofibers by an in situ chemical oxidative polymerization method. The resultant PANI/PMMA fibers were characterized by scanning electronic microscopy and Raman spectrum analysis. The conductivity of an individual coaxial PANI/PMMA fiber is about 2.123 S/cm and that of the conducting PANI coating layer is about 21.8 S/cm. The ammonia sensing properties of the samples were tested by means of impedance analysis. The nano-branched PANI fibers can response significantly to low concentration of ammonia due to large specific surface area, and the sensitivity shows good linear relationship to the ammonia concentration of ppm level. These results indicate that nano-branched coaxial PANI fibers are promising candidate for detection of toxic ammonia gas.