The electrochemical synthesis and optical properties of poly(methylsilyne) and a series of poly(cyclohexylsilyne-co-methylsilyne) network copolymers are described. The new polymers, which are not accessible via the Wurtz coupling reaction, are prepared by electrochemical reduction of methyltrichlorosilane, or mixtures of the monomers methyltrichlorosilane and cyclohexyltrichlorosilane, utilizing copper electrodes in a one-compartment cell. The polymers have optical properties expected for polymers in this class of materials. The poly(methylsilyne) is proposed as a potential soluble precursor for SiC.