In this article, we report chemical oxidative polymerization of 3-methylthiophene (3MTh) in a concentrated TiO2/CHCl3 homogeneous suspension with an oxidant/monomer mole ratio of 3 at room temperature. According to the scanning electron microscopyimages, in this condition, poly(3-methylthiophene) (P3MTh) was prepared with fibrous morphology decorated by nanodimensional TiO2 particles. P3MTh/TiO2 was also characterized by Fourier transform infrared spectroscopy and X-ray diffraction techniques. It was found that no aggregation of nanoparticles occurred during the polymerization process. In addition, the thermal stability of P3MTh/TiO2 nanocomposite was investigated by thermogravimetric analysis and compared with that of an analogously prepared neat P3MTh. The thermal degradation of P3MTh in the temperature range of 300–550°C decreases significantly due to the presence of the TiO2 nanoparticles in the polymer composite.