The published data on the reactions of alcohols, thiols and various nitrogen-containing compounds with acetylene, resulting in the corresponding vinyl derivatives, are considered. The attention is focused on the application of convenient acetylene sources. Other modern approaches to the synthesis of vinyl derivatives are described in detail, including vinyl exchange and metathesis reactions, various types of cross-coupling and cleavage of organic compounds. Some specific synthetic routes to vinyl ethers, vinyl sulfides and enamines are presented in the last Section.