Glycooligomers and glycopolymers (glycocompounds) play important roles in maintaining homeostasis in biological systems. Glycobiology is a burgeoning area in the elucidation of biological systems for which the molecular design of glycocompounds requires further diversification, including both natural and unnatural glycocompounds. Herein, we proposed a synthesis strategy based on the chain polymerization of deliberately designed sugar monomers. Unnatural oligoaminosaccharides comprising N-1,2-glycosidic bonds were synthesized without enzymes through the cationic ring-opening polymerization of 2-oxazoline-based heterobicyclic sugar monomers. To achieve this, a heterobicyclic monomer [Glc(MeOx)], comprising protected glucosamine (GlcN) and 2-methyl-2-oxazoline (MeOx) rings, was designed. This monomer was polymerized using a binary initiating system of tert-butyl iodide (t-BuI) and GaCl₃ to afford oligo[Glc(MeOx)]. The resulting structure corresponded to the condensation product of GlcN with N-1,2-glycosidic bonds. After deprotection of oligo[Glc(MeOx)], the resulting oligoaminosaccharide had a secondary structure different to that of protected oligo[Glc(MeOx)]. Owing to the N-1,2-glycosidic bonds, the oligoaminosaccharide was not degraded by chitinase, which hydrolyzes the condensation product of GlcN with O-1,4-glycosidic bonds.