Conducting polymers, such as polyaniline (PAn), poly-N-methylpyrrole (PNMPy), and copolymers of aniline and N-methylpyrrole P(An-NMPy), have been prepared and compared by chemical and electrochemical methods. The homopolymers and copolymers obtained were characterized with cyclic voltammetry, differential scanning calorimetry, UV–visible, and FT-IR spectroscopy. The UV–visible results showed the intermediate spectroscopic behavior between homopolymers and copolymers. The FT-IR spectra of the resulting copolymers revealed great differences to those of PAn and PNMPy. The conductivity and morphology of the obtained samples were examined by four-point probe apparatus and the scanning electron microscope, respectively. The results indicate a non-linear function of chemical composition and increase the resistivity with NMPy component in P(An-NMPy). The copolymers prepared with more aniline or N-methylpyrrole component have similar morphologies, structures, thermal, and electrochemical performances, and the relative molar ratio of An and NMPy monomers during the polymerization is crucial to the properties of the resulting copolymers.