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Heteroatom polysilylenes with Cl, OR and NR2 substituents attached to the silicon chain through the heteroatom are described. The relationship between the single crystal X-ray structures of octachlorocyclotetrasilane Si4Cl8 and perchloropolysilylene, (SiCl2)n, is discussed with reference to possible mechanisms for its phototopochemical synthesis from Si4Cl8. Substitution with alcohols yields the bis(alkoxy)polysilylenes, and the origin of the red-shifted UV spectra are discussed in terms of the electronic interaction between oxygen n and silicon σ orbitals. Substitution with secondary amines yields soluble, yellow polymers with even longer wavelength UV absorption maxima. Effects of the alkyl chain length on hydrolytic stability are considered.