In this study, N-pyrrole (Py), N-phenylpyrrole (PhPy), and 1[4-methoxyphenyl]-1H-pyrrole (MPhPy) homopolymers were synthesized electrochemically onto carbon fiber microelectrodes (CFMEs). The influences of the substituent effect on electrochemical impedance spectroscopy (EIS) were studied comparatively. All the monomers were electrodeposited in 0.05 M tetraethyl ammonium perchlorate (TEAP)/dichloromethane (CH2Cl2) solution and characterized by cyclic voltammetry (CV), Fourier transform infrared reflectance spectrophotometry (FTIR-ATR), scanning electron microscopy (SEM), and atomic force microscopy (AFM). The morphological study reveals that the polymers were deposited as a continuous and well adhered film to surface of the CFME. An equivalent electrical circuit for three different monomers on CFMEs was proposed and experimental data were simulated to obtain the numerical values of circuit components. All results support the high quality film deposition that resulted in desired electronic properties due to the electron donating behaviors of substituent group of phenyl and methoxy. (c) 2008 Elsevier B.V. All rights reserved.