Electropolymerization of 3,4-(2-benzylpropylene)-dioxythiophene (ProDOT-Bz) on (similar to 7 mu m diameter) single carbon fiber microelectrodes (SCFMEs) in different electrolytes resulted the network of nanofiber structure. Electropolymerization performed in different electrolytes by using cyclo-voltammetric technique. Surface morphology of coatings was investigated by Scanning Electron Microscopy (SEM), the attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) was used for the characterization. A linear relationship between peak currents of films with polymerization charge, and capacitances and coating thickness were obtained. The size of nanofiber network (and pores) can be controlled by the scan rate of the cyclovoltammetric process. Electrochemical impedance spectroscopic investigation of these nanostructures has been indicated the capacitive behavior of electrode system. Electrochemical Impedance Spectroscopic characterization (Capacitance) of the PProDOTBz/SCFME consisting cell was simulated at applied potential and parameters explained by equivalent circuit modeling.