A general and practical protocol for the tertiary-amine-catalysed synthesis of β-alkoxyacrylates from primary, secondary, and tertiary alcohols is described. Of the currently used catalysts, DABCO proved to be the best one for this process. Three factors seem to influence the outcome of the reaction: (1) the nucleophilic strength of the catalyst, (2) the electrophilicity of the intermediate ammonium acrylate, and (3) the pKa/nucleophilicity of the alcohol/alkoxide nucleophile. Reactivity tuning enables the transformation of a range of tertiary alcohols into the corresponding β-alkoxyacrylate derivatives. Differences in the reactivity of different types of alcohol allow the selective transformation of diols containing two different hydroxy groups into the corresponding monoprotected derivatives. This protocol will aid other synthetic organic chemists to easily prepare such vinyl ethers under atom-economic, efficient, and bench-friendly reaction conditions.