Alkene difunctionalization represents one of the most efficient methods for the construction of highly functionalized products from simple and readily available starting materials. These transformations are usually promoted by a highly reactive electrophilic reagent (e.g., peracid, metal oxide, and hypervalent iodine), which engages the unactivated π electrons of the alkene to form two new vicinal chemical bonds in either a concerted or a stepwise fashion. The requirement for these highly reactive electrophiles can often lead to functional group compatibility issues, which may limit their broad use in late-stage synthesis. In addition, many of these reagents generate substantial amounts of byproducts upon reaction. Herein, we describe the development of alkene difunctionalization reactions via electrochemical generation of radical intermediates without the use of highly reactive oxidants or production of wasteful byproducts.