Pyrolytic carbon films (PCFs) were deposited on graphite substrates by methane pyrolysis at temperature range of 1000-1100 degrees C. The fundamental electrochemical behaviors in relation to the surface microstructural properties were investigated to ascertain the potential use of these carbon film electrodes for electroanalytical applications. Cyclic voltammetry were performed to examine the residual current and capacitance and the kinetics parameters were obtained in the presence of Fe(CN)(6)(3-/4-) as a model redox system. Beside, the effects of electrochemical pretreatment were examined using cyclic voltammetry and electrochemical impedance spectroscopy. Fe(CN)(6)(3-/4-), Co(phen)(3)(3+/2+), Fe3+/2+, and hydroquinone were the redox systems employed to evaluate the electrochemical behavior of the PCF electrodes after pretreatment. Raman spectroscopy, scanning electron microscopy (SEM), and polarized light optical microscopy (PLOM) were carried out to explain the microstructural and morphological properties. Low and stable residual currents toward anodic activation and high electron transfer kinetics specifically after anodic activation were the attractive features of those carbon film electrodes prepared at the higher part of the processing temperature range. (C) 2012 Elsevier B.V. All rights reserved.