Micron sized single carbon fibers were cyclovoltammetrically coated with poly[3.4-(2,2dibenzylpropylenedioxy)thiophene] resulting in a nanofiber network at the surface. The method provides conjugated polymer nanostructures covalently and uniformly bound to micron sized substrates. When the electropolymerization is carried out with different electrolytes in acetonitrile the dopant influences the structure of the coating layer what is proved by electrochemical impedance spectroscopy and electron microscopy. Electrodes based on poly[3,4-(2,2-dibenzylpropylenedioxy)thiophene] on single carbon fiber microelectrodes (SCFMEs) prepared in Bu(4)NPF(6)/ACN show the best capacitance performance due to their higher surface area. The improvement is attributed to the formed nanofiber network structure which results in a more efficient charge transport and collection.