This review discusses the advancements in synthetic organic electrochemistry since 2000, focusing on enabling methods and their synthetic applications. Electrochemistry, a fundamental and ancient form of chemical reaction, involves the addition or removal of electrons through electrical potential. The history of electroorganic chemistry dates back to 1800 with the invention of the Volta Pile, and Faraday's work in the 1830s laid the foundation for systematic studies. Key developments include the introduction of terms like "electrolysis," "anode," and "cathode," and the use of ionic salts as electrolytes. The review highlights the evolution of electrochemical setups, from galvanostatic conditions to potentiostatic conditions, and the introduction of equipment like potentiostats and voltammetry techniques. Electrochemical reactions are categorized into oxidations (anodic), reductions (cathodic), and paired electrolysis. The focus is on functional group transformations and the use of mediators to enhance reactivity and control selectivity. Oxidations, such as the Kolbe reaction, involve the anodic oxidation of carboxylates to form alkyl radicals, which then dimerize to form C–C bonds. Other oxidations include the oxidation of sulfonic acid salts, amines, and amides to form N-centered radicals and nitrenes. The Shono oxidation, a classic reaction, involves the anodic oxidation of amides and carbamates to form N-centered radical cations, which can be trapped by nucleophiles to form various products. The review also discusses the use of electroauxiliaries to control chemo- and regioselectivity in the Shono oxidation, and the generation of acyliminium cation pools to enhance the scope of reactions. These cation pools can engage with nucleophiles to form C–C bonds, and they have found applications in various synthetic transformations, including combinatorial organic syntheses and living polymerization. Overall, the review emphasizes the synthetic potential and environmental benefits of electrochemical methods, highlighting their role in the synthesis of complex molecules and their applications in drug discovery and natural product synthesis.This review discusses the advancements in synthetic organic electrochemistry since 2000, focusing on enabling methods and their synthetic applications. Electrochemistry, a fundamental and ancient form of chemical reaction, involves the addition or removal of electrons through electrical potential. The history of electroorganic chemistry dates back to 1800 with the invention of the Volta Pile, and Faraday's work in the 1830s laid the foundation for systematic studies. Key developments include the introduction of terms like "electrolysis," "anode," and "cathode," and the use of ionic salts as electrolytes. The review highlights the evolution of electrochemical setups, from galvanostatic conditions to potentiostatic conditions, and the introduction of equipment like potentiostats and voltammetry techniques. Electrochemical reactions are categorized into oxidations (anodic), reductions (cathodic), and paired electrolysis. The focus is on functional group transformations and the use of mediators to enhance reactivity and control selectivity. Oxidations, such as the Kolbe reaction, involve the anodic oxidation of carboxylates to form alkyl radicals, which then dimerize to form C–C bonds. Other oxidations include the oxidation of sulfonic acid salts, amines, and amides to form N-centered radicals and nitrenes. The Shono oxidation, a classic reaction, involves the anodic oxidation of amides and carbamates to form N-centered radical cations, which can be trapped by nucleophiles to form various products. The review also discusses the use of electroauxiliaries to control chemo- and regioselectivity in the Shono oxidation, and the generation of acyliminium cation pools to enhance the scope of reactions. These cation pools can engage with nucleophiles to form C–C bonds, and they have found applications in various synthetic transformations, including combinatorial organic syntheses and living polymerization. Overall, the review emphasizes the synthetic potential and environmental benefits of electrochemical methods, highlighting their role in the synthesis of complex molecules and their applications in drug discovery and natural product synthesis.