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Unlike linear and hyperbranched counterparts, densely\u2010packed hydroxyl and ether groups in 4th\u2010generation dendritic polyglycerol interact with the ions, activating the formation of hydrogen bonding at the ice interface. By inhibiting both intra\u2010 and extracellular ice growth and recrystallization, this biocompatible dendritic polyglycerol proves highly effective as a cryoprotectant; hence, achieving the cell recovery rates of \u2248134\u2013147%, relative to those of 10% dimethyl sulfoxide, which is a conventional cryoprotectant for human tongue squamous carcinoma (HSC\u20103) cell line and human umbilical vein endothelial (HUVEC) cells. Further, it successfully recovers the network\u2010forming capabilities of HUVEC cells to \u224889% in tube formation after thawing. 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