Polyaniline (PANI) nanofibers were synthesized by interfacial polymerization method and p-toluene sulfonic acid was used as a dopant to enhance the conductivity of the resultant emeraldine base of PANI. A blend of PANI and poly(styrene-co-acrylonitrile) (SAN) in the form of nanofibers was electrospun on interdigitated copper electrode and was used for sensing of ammonia and nitrogen dioxide. The sensor exhibited excellent sensitivity and responded quickly to those gases at ppm levels as low as 10. Transmission electron microscopy (TEM) and Fourier transform infrared (FTIR) spectroscopy results revealed that there is a good molecular level interaction between PANI and SAN, which is believed to be the major reason for the excellent gas sensitivity of these blend nanofibers.