A photoredox-copper dual-catalyzed cross dehydrogenative coupling reaction of glycosides with benzylic C-H substrates has been developed.The reaction proceeds smoothly under mild reaction conditions and features the using of readily accessible starting materials, which allows the highly site-selective synthesis of diverse glycosides O-alkylation products in 27%~72% yields, providing a new synthetic tool for the site-selective modification of glycosides.Keywords photoredox catalysis;