As naturally abundant and recyclable industrial feedstock, alcohols and carboxylic acids have drawn tremendous attention in medicinal chemistry and polymer chemistry. The selective C-O cleavage of the hydroxyl group represents an appealing strategy to deliver alkyl and carbonyl moieties into organic molecules. Classical examples of hydroxyl activation include the Appel reaction, Mitsunobu reaction, and Barton-McCombie deoxygenation. However, these early approaches still require large amounts of oxidants or reductants, and suffer from harsh conditions and low atom economy. Electrosynthesis has proven to be an effective and mild way of the modern chemical industry, avoiding the use of chemical oxidants/reductants through the action of an electric current. In this review, we have summarized the recent advances in electrochemical deoxygenation reactions and categorized the deoxygenation methods by different functionalities.