PVA-based hydrophilic monoliths have potential applications in area of life science on account of their great hydrophilicity and biocompatibility. To prepare PVA-based hydrophilic monoliths, PVAc-based polyHIPEs were first prepared through the method of high internal phase emulsion (HIPE) template, in which polyglycerol polyricinoleate was used as a surfactant to effectively inhibit Ostwald ripening and coalescence and triallyl isocyanurate was used as a crosslinking agent to increase the chain rigidity and to provide reaction sites for alcoholysis. After alcoholizing the PVAc-based polyHIPEs, the PVA-based monoliths were successful prepared, which was confirmed by the results of FTIR. Results of investigation of the surface area, average void diameter, average interconnection diameter and average pore diameter of both of the PVAc-based and the PVA-based polymers by the BET method show that removing of easter groups from PVAc-based one resulted in a open-cell and a highly interconnected porous structure in PVA-based one. Results of contact angle measurements confirmed that PVA-based monoliths exhibited a strong hydrophilicity. The biocompatibility of the polymer will be investigated in the following study.