A multifunctional O-phenyl thiocarbonyl (O(C═S)OPh) group was introduced in glycosylation reactions. This auxiliary group exhibits three features (1) C6-long-range participation effect, (2) relay activation, and (3) switchable promoter-controlled carbonylation, which enables the facile synthesis of both 6-deoxy glucoside and 6-alcohol glucoside. In addition, we successfully quantified the extent of the C6-acyl participation effect and developed its application toward the α-trisaccharide motif.