Olefins are important substructures in synthetic organic chemistry, polymer chemistry and medicinal chemistry, and are omnipresent in natural products and pharmaceuticals. Also Cvinyl glycosides, which are a central class of vinylated carbohydrates, are present in many natural products and pharmaceuticals. While transition metal catalysis is ubiquitous in alkene synthesis, the achievement of high regio-and stereoselectivity, as well as broad functional group tolerance, constitute some of the main synthetic challenges. Visible-light mediated photocatalysis has in recent years become an impressive strategy for the synthesis of complex organic molecules, enabling novel reaction pathways and mild reaction conditions. Indeed, photocatalytic synthetic routes to olefins have been investigated extensively, and commonly involve a transition metal-catalyzed cross-coupling between alkyl/aryl halides or styrenes and alkylation radical precursors such as carboxylic acids, 4-alkyl-dihydropyridines (4-alkyl-DHPs) or alkyl silicates (Scheme 1a). To achieve high yields, a dual catalytic system with ligands and external oxidants is generally required. The synthesis of C-vinyl glycosides has also been performed photocatalytically, but generally relies on a significant number of protection and deprotection steps, dual catalytic systems, elevated temperature, Grignard or dialkylzinc reagents and often employ ligands (Scheme 1b). In recent years, vinylbenziodoxolones (VBX) have received significant attention as potent vinylating reagents. VBX reagents are easily synthesized in one-pot from 2-iodobenzoic acid, and Scheme 1. Photocatalytic vinylations.