In conclusion, we have reported a transition metal-free photoredox-catalyzed cross-coupling reaction of VBX with alkyl-DHPs. The reaction conditions are mild and the method tolerates common functional groups, producing straightforward access to corresponding alkenes in good to high yields with retention of the alkene configuration. The method was also applied to 4-glycosyl-DHPs, resulting in a diastereoselective synthesis of vinyl Cglycosides with excellent E/Z ratios in good yields. The method opens up a novel synthetic strategy to synthesize trisubstituted enamides and enol ethers with excellent stereoselectivity. Preliminary mechanistic studies support the involvement of a concerted radical coupling as the key step. Given the uncomplicated synthesis of the starting materials and simple reaction setup, we anticipate that the protocol will find broad applications in the synthesis of di-and trisubstituted alkenes and a variety of pharmaceutically important C-vinyl/alkynyl glycosides.