Herein, we report a new approach to fabricate polyvinyl alcohol (PVA) based hydrophilic monoliths by alcoholysis of porous emulsion-templated polyvinyl acetate (PVAc). The precursory PVAc-based monolith is obtained by polymerization of a W/O high internal phase emulsion (HIPE) containing vinyl acetate as the external phase while water as the internal phase. As an alcoholysis-stable tri-functional commonomer, triallyl isocyanurate is chosen as the crosslinking agent to prevent possible collapse of the polymeric skeleton and the consequent losses in mechanical properties during the alcoholysis step. By alcoholysis of the resulting PVAc-based monolith, the PVA-based monoliths are successful prepared as confirmed by FTIR analysis. BET analysis and SEM observation confirm the formation of open-cell and highly interconnected porous structures of PVA-based monoliths with surface areas of around 16 m2/g. Stemming from the intrinsic hydrophilicity of hydroxyl and morphology, PVA-based monoliths exhibit great enhancement in hydrophilicity with a much lower water contact angles than that of PVAc-based monoliths. (C) 2017 Elsevier Inc. All rights reserved.