Well-confined uniform polyaniline (PANT) nanofibers were synthesized by using photo-assisted chemical oxidative polymerization of aniline in the presence of different dopant acids, and the radical scavenging ability of the produced PANI nanofibers was determined by the DPPH assay. It was found that the antioxidant activity of PANI nanofibers was higher than conventional PANI,and increased with decreasing of averaged diameter of the nanofibers. The enhanced antioxidant activity was concerned with increased surface area of PANI nanofibers.