Vinyl ethers bearing the fragment RO–CH=CH2, where R is an alkyl or aryl substituent, are valuable substrates for organic synthesis and polymer chemistry. The double carbon–carbon bond is highly reactive and can be used in a wide variety of organic transformations, including addition processes—particularly cycloaddition and polymerization reactions. Recent investigations in this field have demonstrated the significant potential of subsequent transformations: vinylation of alcohols, cycloaddition of vinyl ethers, and alcohol release. Combination of these processes enables the introduction of a C2 fragment into a wide range of organic molecules. Due to these advancements, vinylation of alcohols has become a cornerstone in organic synthesis. This review focuses on an overview of important approaches to the vinylation of alcohols and highlights recent achievements in this field.