The pursuit for the electrosyntheses of high quality polycarbazole (PCz) films is a great challenge for the application of polycabazoles. The incorporation of thiophene unit into carbazole monomer might result in a novel polymer having both the advantages of polythiophene and polycarbazole. As expected in this paper, a novel conducting polymer, free-standing poly(9-(6-(thiophene-3-yl)hexyl)-9H-carbazole) (PTh-H-Cz) films with electrical conductivity of 7.8 S/cm, were synthesized electrochemically by direct anodic oxidation of a novel carbazole monomer, 9-(6-(thiophene-3-yl)hexyl)-9H-carbazole (Th-H-Cz), in boron trifluoride diethyl etherate (BFEE) solution. Incorporation of thiophene unit into carbazole monomer as a pendant led to the electrodeposition of high quality PCz films with metallic shine. Fluorescence spectral study revealed that as-formed polymer film in solid state was a good blue light emitter with strong emission at about 410 nm. This high quality free-standing PTh-H-Cz film will facilitate their potential applications as blue-light-emitting materials in organic light-emitting dioxide.