Radical Deoxyfunctionalisation Strategies**

Abstract Due to their abundance and readily available synthesis, alcohols provide ideal handles for the selective derivatisation of organic molecules. Radical chemistry offers versatile strategies for the conversion of Csp 3 −O bonds into a wide range of Csp 3 −C, Csp 3 −H, or Csp 3 −heteroatom bonds. In these reactions, alcohols are readily derivatised with an activator group which can undergo facile mesolysis to generate a primary, secondary, or tertiary open‐shell species that can engage in further transformations. These strategies are particularly effective at overcoming steric limitations associated with nucleophilic substitution pathways. Despite their potential, the use of radical deoxyfunctionalisation reactions as a general strategy for the synthesis of useful and complex molecules remains underutilised. In this Review, we highlight recent advancements in this exciting field in which photocatalysis, transition metal catalysis or electrochemistry are used to initiate the radical processes.