A　highly　efficient　coupling　of　glycosyl　stannanes　and　sulfonium　salts　enabled　by　synergistic　Pd/Cu　catalysis　is　disclosed,　facilitating　the　construction　of　C　-aryl/alkenyl　glycals　under　mild　conditions　in　high　yields.　The　protocol　tolerates　a　wide　scope　of　functional　groups　including　ketone,　cyano,　ester,　amide,　nitro,　halide.　The　one-pot　formal　C　-H　glycosylation　starting　from　arene　is　demonstrated　with　a　reaction　sequence　of　dibenzothiophenylation/Stille　coupling.　Besides,　a　gram-scale　reaction　is　performed　successfully,　showing　the　high　applicability　of　this　protocol.(c)　2023　Published　by　Elsevier　B.V.　on　behalf　of　Chinese　Chemical　Society　and　Institute　of　Materia　Medica,　Chinese　Academy　of　Medical　Sciences.