Sustainable Photoelectrochemical Geminal α‐Fluorosulfenylation of Diazo Compounds through Carbene Radical Anion Intermediate

α‐Fluorosulfenyl compounds are privileged building blocks found in pharmaceuticals and agrochemicals. While the geminal difunctionalization of diazo compounds with two different nucleophiles under mild and sustainable conditions can be envisioned as a versatile method for constructing α‐fluorosulfinyl molecules, it remains a significant unmet challenge. Herein, geminal α,α‐difunctionalization of diazo compounds by merging sustainable photo‐ and electrocatalysis is presented. A wide range of α‐fluorosulfinyl products are synthesized using commercial ionic liquid as a fluorine source with moderate to good yields and excellent selectivities. Several experiments are performed to detail the reaction mechanism and elucidate the cooperativity of photo‐ and electrocatalysis in facilitating the reaction under milder, safe, and green conditions.