We report the one-pot synthesis of hyperbranched polyethers possessing amino functionality by using a Boc-protected butanolamine glycidyl ether monomer (BAG). A series of hyperbranched Boc-protected polyamino glycerols (PBAG) was prepared through anionic ring-opening multibranching polymerization to yield PBAG with controlled molecular weights (2300-14700 g/mol) and relatively low molecular weight distributions. Subsequent deprotection of PBAG yielded hyperbranched polyaminoglycerols (PAG) possessing a globular polymeric structure that comprise of ran¬domly branched structure with a large number of amine and hydroxyl groups. 1H- and 13 C-NMR, GPC and MALDI-TOF measurements confirmed the successful polymerization of the hyperbranched PAG polymer. With its superior biocompatibility of PAG, we anticipated the prospective potentials in biological and biomedical fields.