A　novel　and　efficient　method　for　the　stereoselective　and　stereodivergent　synthesis　of　both　unprotected　and　protected　styryl　C-glycosides　through　the　reaction　of　sodium　glycosyl　sulfinate　and　hypervalent　styryl　iodine　reagents　is　described.　Using　2-bromo-9-fluorenone　as　a　photocatalyst,　C-styryl　glycosides　with　an　E　configuration　were　selectively　obtained.　Furthermore,　the　introduction　of　a　newly　designed　iridium-based　catalyst　enabled　the　selective　formation　of　glycosides　predominantly　in　the　Z　configuration.　Mechanistic　studies　reveal　the　glycosyl　radical　is　involved　in　the　transformation.