An efficient electrochemical radical silyl‐oxygenation of electron‐deficient alkenes is demonstrated, which gives access to a variety of new highly functionalized silicon‐containing molecules, including β‐silyl‐cyanohydrin derivatives in good yields with excellent chemo‐ and regio‐selectivity. This electrochemical radical silylation process conducts under mild conditions without the use of transition metal catalyst or chemical oxidant and exhibits a wide scope of substrate silanes with high functional‐group tolerance. The ability to access silyl radicals using electrochemical Si−H activation offers new perspectives for the synthesis of valuable organosilicon compounds in a sustainable and green manner.