This study aims to synthesize poly(methylsilyne) by electrochemical reduction of methyltrichlorosilane at a constant potential of -6 V, while investigating the effects of parameters such as the nature of the electrode, solvent and supporting electrolyte, the monomer/solvent ratio, and the reaction time on the properties of the products. The polymer was characterized by H-1-NMR (Proton Nuclear Magnetic Resonance Spectroscopy), FTIR (Fourier Transform Infrared Spectroscopy), UV-Visible Spectroscopy, and TGA (Thermogravimetry Analysis). Copper (Cu) electrodes were used as stainless steel introduced impurities into the system. In an electrolytic media consisting of acetonitrile (AN), sodium dodecyl sulfate (SDS), and Cu electrodes, increasing the monomer/solvent ratio and the reaction time affected the system negatively based on the purity of poly (methylsilyne) in the final product. Reproducible results were only achieved in an electrolytic media containing 1,2-dimethoxyethane (DME) and tetrabutylammonium perchlorate (TBAP). In this system, the purity of the products was less dependent on monomer/solvent ratio and reaction time. The color and the H-1-NMR, FTIR, and UV-Visible spectra proved that the product is poly(methylsilyne). In addition, the significantly high-average decomposition temperature obtained from TGA results revealed that the polymer is a good candidate as an additive for improving thermal stability and flame retardancy in thermoplastics. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 118: 3049-3057, 2010