We report the first example of grafting hyperbranched polyglycerol onto poly(vinyl alcohol) via ring-opening polymerisation of glycidol to prepare poly(vinyl alcohol-graft-hyperbranched glycerol) (P[(VA)-g-(hPG)]). The effects of catalyst, molecular weight of PVA, reaction temperature, water content, moles of reagent, and addition time of reagent were also investigated. P[(VA)-g-(hPG)] with various mole fractions of hPG were prepared and the degrees of substitution and branching were determined. P[(VA)-g-(hPG)] displayed decreased degree of crystallinity and also increased solubility in water, compared to PVA. P[(VA)-g-(hPG)] is shown to be a superior hair styling polymer with a curl retention value of 85% after 4 h. (C) 2017 Wiley Periodicals, Inc.