The synthesis of 9-(4-vinylbenzyl)-9H-carbazole (VBCz) monomer and surface characterizations of thin film coating of poly(9-(4-vinylbenzyl)-9H-carbazole), P(VBCz) homopolymer on carbon fiber microelectrode (CFME) was performed. Coatings of polymer thin films obtained, with different initial monomer concentrations, were characterized by cyclic voltammetry, scanning electron microscopy and Fourier transform infrared reflectance-attenuated total reflection spectroscopy. Different initial monomer concentrations (1, 3, 5, and 10 mM) were electrodeposited in 0.1 M lithium perchlorate/acetonitrile solution. The characterization of the thin polymer films was performed on the surface of carbon fiber, and composition of polymeric structure was proposed. Capacitor behavior of modified CFME was studied by electrochemical impedance spectroscopy. The deposition charge of polymer growth affected the redox parameters of resulting coated CFME.