In this work, low molecular weight hyperbranched polyglycerols (LMPGs) are synthesized in bulk using ascorbic acid as an activator. Different molar ratios of glycidol and ascorbic acid were mixed and stirred at ambient conditions and LMPGs with different molecular weights, degree of branching and relative abundance of the structural units were obtained. According to spectroscopy data, ascorbic acid was not incorporated in the structure of the polymer and plays the role of activating agent in the polymerization process. In this synthetic protocol, no other chemical reagents and organic solvents were used. Therefore, products are free of toxic impurities and suitable for future biomedical applications.