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Stimulus-responsive hydrogels, which can undergo significant physicochemical changes in response to various physical or chemical stimuli, have drawn wide attention in many fields. In this study, novel photoresponsive hydrogels prepared by free radical copolymerization of xylan-type hemicellulose methacrylate with 4-[(4-acryloyloxyphenyl)azo]benzoic acid (AOPAB) were investigated, which showed multiresponsive behaviors to pH, water/ethanol alternating solutions, and light. The swelling ratios of the prepared hydrogels in distilled water decreased from 9.8 to 2.2 g/g with AOPAB content increase from 2% to 16%. The hydrogel displayed rapid swelling and deswelling performance in water and ethanol alternating solutions. Additionally, under UV irradiation the trans-conformation of azobenzene in the hydrogel would generally convert into the cis-conformation and resulted in the hydrophilic/hydrophobic balance variation of the hydrogel. Therefore, the hydrogel loaded with vitamin B12 (VB12) showed a higher drug cumulative release rate under UV irradiation than that without UV irradiation.