Copolymer films of N-methylpyrrole (N-MPy) and N-methylcarbazole (N-MCz) were synthesized electrochemically onto single carbon fiber microelectrodes (CFMEs). Deposition conditions on the carbon fiber, influence of the monomer concentrations on the copolymerization of P[N-methylpyrrole-co-N-methylcarbazole] P[N-MPy-co-N-MCz], and the electrochemistry of the resulting homopolymer and copolymers were studied using cyclic voltammetry, FTIR-ATR, in-situ spectroelectrochemistry, a UV-vis spectrophotometer, and a 4-point probe conductometer. The effects of current density, supporting electrolyte type, temperature, and monomer concentrations on the formation of the film were studied. Redox parameters and stability of charged films were obtained by cyclic voltammetry. The most stable copolymer was obtained in lithium perchlorate-acetonitrile electrolytic solution (LiClO4/ACN).