The reactions between silicon difluoride and propyne, propyne-d1, 1-butyne, 2-butyne, and 3,3-dimethyl-1-butyne were studied. In each case products resulting from combining ratios (SiF2:alkyne) of 2:1 and 2:2 were isolated and identified. The 2:1 compounds were shown to be derivatives of disilacyclobutene, while three types of 2:2 compounds were identified. These either had an open chain structure, resulting from migration of either α (to C≡C)—CH or acetylenic H, or were derivatives of disilacyclohexadiene. Rationalizations of the types of products found and of the conditions which affect the reaction mechanism are discussed.