We report a one-pot synthesis of hyperbranched polyglycerols possessing amino functionality by using a novel Boc-protected aminoethanol glycidyl ether monomer (BAG). A series of hyperbranched Boc-protected polyamino glycerols (PBAG) were prepared through a one-pot anionic ring opening multibranching polymerization to yield PBAG with controlled molecular weights (3500-17400 g/mol). Subsequent deprotection of PBAG yielded hyperbranched polyamino glycerols (PAG) with a globular polymeric structure that comprises a randomly branched structure with a large number of functional amine and hydroxyl groups. H-1, C-13, and N-15-NMR, GPC, and MALDI-TOF measurements confirmed the successful polymerization of the hyperbranched PAG polymers. With its superior biocompatibility of PAG, we anticipate the prospective potentials for the applications in biological and biomedical fields. (c) 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 4013-4019