The synthesis of gamma-methoxypropylmethyldichlorosilane, and its subsequent polymerization and copolymerization with di-n-hexyldichlorosilane through the reductive coupling with sodium has been accomplished. The resulting polymers contain methyl ether side groups that allow further synthetic transformations on the polysilane backbone. For poly (gamma-methoxypropylmethylsilylene) these groups impart solubility characteristics different than typical alkyl and aryl substituted polysilanes. These new polymers and copolymers have been characterized by GPC and H-1-, C-13-, and Si-29-NMR.