A series of polysilanes was prepared by the alkali metal dechlorination of chlorosilane monomers, in which the overall functionality, F, of the reaction was varied. Starting monomers of functionality f = 2.0 and 3.0 were reacted together in various proportions to achieve values of F of 2.2, 2.35, and 2.5. In addition to varying the functionality of the reaction, three different difunctional monomers, dimethyldichlorosilane (DMDCS), diphenyldichlorosilane (DPDCS), and methylphenyldichlorosilane (MPDCS), and two trifunctional monomers, phenyltrichlorosilane (PTCS) and ethyltrichlorosilane (ETCS), were used. The effect of these changes on the yields of the polysilanes was determined, and the products were investigated by the use of thermogravimetry (TG), gel permeation chromatography (GPC), and thermomechanical analysis (TMA). The ability to spin a polysilane fiber was also assessed.