Photocrosslinked hyaluronic acid/poly(vinyl alcohol)-styrylpyridinium (HA/PVA-SbQ) hydrogels were synthesized for controlled antitumor drug delivery. The photocrosslinking reaction was rapid, and the time required for completely converting into the insoluble hydrogels was less than 500 s on exposure to 5 mW/cm2 UV light irradiation. The resulting hydrogels exhibited sensitivity to the pH value of the surrounding environment. Scanning electron microscopic analysis revealed that the morphology and the pore size of the hydrogels could be controlled by changing the ratio of HA and PVA-SbQ in the formulations. Paclitaxel (PTX)-loaded hydrogel could also be formed rapidly by UV irradiation of a mixed solution of HA/PVA-SbQ and PTX. Release profiles of PTX from the hydrogels showed pH-dependent and sustained manner. Moreover, our data revealed that PTX released from the HA hydrogels remained biologically active and had the capability to kill cancer cells. In contrast, control groups of HA hydrogels without PTX did not exhibit any cytotoxicity. This study demonstrates the feasibility of using HA-based hydrogels as a potential carrier for chemotherapeutic drugs for cancer treatments. (c) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012