The surfaces of polyacrylonitrile-based carbon fibers were treated by an electrochemical anodic method. Three different kinds of ammonium-salt solutions namely NH4HCO3, (NH4)(2)CO3 and (NH4)(3)PO4 were respectively chosen as the electrolytes. The effect of these electrolytes on the surface structure was studied by scanning electron microscopy (SEM), atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS). The results showed that longitudinal grooves on the fiber surface became more well-defined and much deeper after surface treatment, and the root mean square roughness (RMS) of carbon fiber surface increased from 4.6 nm for untreated fibers to 13.5 nm for treated fibers in (NH4)(3)PO4 electrolytes. The concentration of oxygen and nitrogen atomic on the fiber surface increased after surface treatment. The tensile strength of oxidized fibers had an obvious decrease, whereas the interlaminar shear strength (ILSS) value of corresponding carbon fiber reinforced polymers (CFRPs) increased in a large extent. The intensity of oxidative reaction varied with the change of ammonium-salt solutions and electrochemical oxidation in (NH4)(3)PO4 electrolyte was of the most violence. The corresponding mechanism was also discussed and the result showed that the higher the concentration of OH-ions in the electrolytes, the violent the oxidative reaction happened. (C) 2012 Elsevier B.V. All rights reserved.