Sialic acid is a sugar residue present in many biologically significant glycans of mammals, commonly as a terminal alpha-glycoside. The chemical structure of sialic acid, which features an anomeric center with carboxyl and methylene substituents, poses a challenge for synthesis of the alpha-glycoside, thus impeding biological and therapeutic studies on sialic acid-containing glycans. We present a robust method for the selective alpha-glycosidation of sialic acid using macrobicyclized sialic acid donors as synthetic equivalents of structurally constrained oxocarbenium ions to impart stereoselectivity. We demonstrate the power of our method by showcasing broad substrate scope and applicability in the preparation of diverse sialic acid-containing architectures.