The copolymerization of dibenzofuran (DBF) and 3-methylthiophene (MeT) was successfully achieved electrochemically by direct anodic oxidation of the monomer mixtures in boron trifluoride diethyl etherate. The effects of applied polymerization potential and the monomer concentration ratios on the copolymerization were investigated by linear sweep voltammetry and cyclic voltammetry (CV). The structure of copolymer films were investigated by UV-Vis, infrared spectroscopy, thermal analysis. As-formed novel copolymers own both the advantages of poly(3-methylthiophene) and poly(dibenzofuran), that is, good redox activity, good thermal stability. Fluorescence spectra suggested that emission spectrum of copolymer films was blue-shifted in contrast to that of PDBF film.