Selective activation of “armed’ and ‘'disarmed” glycal donors enabling the stereo-controlled glycosylations by employing Cu(II)-catalyst as the promoter has been realized. The distinctive stereochemical outcome in the process is mainly influenced by the presence of diverse protecting groups on the donor and the solvent system employed. The protocol is compatible with a variety of aglycones including carbohydrates, amino acids, and natural products to access deoxy-glycosides and glycoconjugates with high α-anomeric selectivity. Notably, the synthetic practicality of the method is amply verified for the stereoselective assembling of trisaccharides comprising 2-deoxy components. Mechanistic studies involving deuterated experiments validate the syn-diastereoselective 1,2-addition of acceptors on the double bond of armed donors.