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A series of pH sensitive semi-interpenetrating polymer network (semi-IPN) structural hydrogels composed of poly(vinyl alcohol) (PVA) and 21-arm star poly[2-(dimethylamino)ethyl methacrylate] (star PDMAEMA) with different molecular weight were prepared. Riboflavin was used as a model drug to evaluate the drug loading capacities and drug release behaviors of the semi-IPN structural hydrogels. The molecular weight of the star PDMAEMA polymers was calculated by GPC, and the formation of semi-IPN structure was confirmed by FTIR and SEM. It was found that the molecular weight of star PDMAEMA has significant effect on the structure, swelling ratio and drug release behaviors of the semi-IPN hydrogel at different pH conditions. The results suggested that the PVA/star PDMAEMA-50,000 hydrogel exhibited highest swelling ratio and drug loading capacity. The pH-sensitive semi-IPN hydrogel based on star PDMAEMA could be a promising drug delivery system due to the controllable porous structure.