In this paper, a facile and efficient method is reported to prepare polyaniline/carbon nanofiber (PANI/CNF) hybrid films by in situ chemical polymerization of aniline. The various morphologies and microstructures of PANI/CNF hybrid films can be controlled by adjusting the concentration of aniline and different acids as the protonation reagent, and the formation mechanism is illustrated in this study. The surface morphologies and chemical structure of the PANI/CNF hybrid films are characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), water contact angle (CA), FT-IR, Raman, and UV-vis spectrophotometers. The different morphology of uniformly coated, twist-tangled, and needle-like PANT built on CNF films are obtained by using HCl, H2SO4, and HClO4 as protonation reagent and the obtained hybrid films are labeled as PANI/CNF-f1, PANI/CNF-f2, and PANI/CNF-f3, respectively. We demonstrated that the different protonation reagent has the determined effect on the surface properties of the obtained hybrid films that can transfer from hydrophilic to hydrophobic. Besides, the various morphologies of PANI play an important role in their electrochemical properties. PANI/CNF-f3 exhibits higher specific capacitance and better stability than that of the PANI/CNF-f1 and PANI/CNF-f2. Considering its unique needle-like structure, this work is a proof of concept that micro-structure and morphology can determine the macro-properties. And this study supplies a facile method to fabricate PANI/CNF hybrid films that can be used as electrode materials in supercapacitors. (C) 2013 Elsevier Inc. All rights reserved.