Camphor sulfonic acid (CSA)-doped polyamide 6/polyaniline (PA6/PANI) composite nanofibers were fabricated using in situ polymerization of aniline under different CSA concentrations (0.02, 0.04, 0.06, 0.08 and 0.10 M) with electrospun PA6 nanofibers as templates. The structural, morphological and ammonia sensing properties of the prepared composite nanofibers were studied using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), four-point probe techniques, X-ray diffraction (XRD) and a home-made gas sensing test system. All the results indicated that the CSA concentration had a great influence on the sensing properties of CSA-doped PA6/PANI composite nanofibers. The composite nanofibers doped with 0.02 M CSA showed the best ammonia sensing properties, with a significant sensitivity toward ammonia (NH3) at room temperature, superior to that of the composite nanofibers doped with 0.04-0.10 mol/L CSA. It was found that for high concentrations of CSA, the number of PANI-H+ reacted with NH3 would not make up a high proportion of all PANI-H+ within certain limits. As a result, within a certain range even though higher CSA-doped PA6/PANI nanofibers had better conductivity, their ammonia sensing performance would degrade.