Hydrosilanes possessing reactive Si-H bond are used in synthesizing various types of polysilanes by dehydrocoupling under the influence of various organometallic promoters. Catalytic Si-Si/Si-O coupling of hydrosilanes with hydrosilanes, alcohols, and lactones to silicon-based polymers are described in this article as selective examples of our recent research developments. These silicon-containing polymers can be used as a precursor to prepare useful functional materials for fabricating electronic devices.