Abstract: Organic polysilanes may be produced in a simpler, safer and more economic manner by reacting an organohalosilicon hydride with lithium metal or lithium-alkali metal alloy. According to the reaction the silicon-silicon bonds of the organopolysilane are formed by the removal of halogen and hydrogen from the hydride. Particularly important is the formation of dodecamethylcyclohexasilane by the reaction of dimethyl chlorosilane with lithium metal. Simpler polysilanes may be produced by adding to the reaction mixture endcappers such as trifunctional organohalosilanes without an Si-H bond.