<p>The deoxygenative radical reaction of alcohols is a critical topic for alcohol functionalization. This reaction involves cleavage of the C-O bond in alcohols, generating diverse alkyl carbon (sp³) radical intermediates. However, the high bond dissociation energy of the C-O bond (about 95 kcal/mol) makes deoxygenative transformation under mild conditions particularly challenging in organic synthesis. In recent years, researchers have successfully accomplished functionalization by selectively cleaving the C-O bonds and developing various strategies for constructing C(sp³)-C and C(sp³)-X bonds, thereby providing crucial pathways for synthesizing target molecules containing alkyl carbon moieties. Consequently, selective deoxygenative transformations of alcohols hold significant potential for advancing synthetic chemistry. This article comprehensively reviews strategies addressing alcohol deoxygenation over the past decade. The most representative strategies for deoxygenation primarily rely on metal-reducing agents, pre-activated generation of active derivatives, or the utilization of activating reagents to accomplish alcohol deoxygenation reactions.</p>