A novel hybrid system has been investigated based on polyaniline/carbon nanofiber (Pani/CNF) electrospun nanofibers for modification of gas diffusion electrode (GDE) in proton exchange membrane fuel cells (PEMFC). Pani/CNF hybrid nanofibers were synthesized directly on carbon paper by electrospinning method. For preparation of catalyst ink, 20wt.% Pt/C electrocatalyst with a platinum loading of 0.4mgcm −2 was prepared by polyol technique. SEM studies applied for morphological study of the modified GDE with hybrid nanofibers. This technique indicated that the electrospun nanofibers had a diameter of roughly 100nm. XRD patterns also showed that the average size of Pt nanoparticles was about 2nm. Subsequently, comparison of the hybrid electrode electrochemical behavior and 20wt.% Pt/C commercial one was studied by cyclic voltammetry experiment. The electrochemical data indicated that the hybrid electrode exhibited higher current density (about 15mAcm −2 ) and ESA (160m 2 gr −1 ) than commercial Pt/C with amount of about 10mAcm −2 and 114m 2 gr −1 , respectively. The results herein demonstrate that Pani/CNF nanofibers can be used as a good alternative electrode material for PEMFCs.