Thermal cross-linking method of poly(vinyl alcohol) (PVA) using poly(acrylic acid) (PAA) was carried out on PVA/PAA hydrogels. The level of gelation was measured in the PVA/PAA hydrogels with various PAA contents. The swelling behavior at various pHs showed that the swelling kinetics and water contents of the PVA/PAA hydrogels reached equilibrium after 30 h, and the time to reach the equilibrium state decreased with increasing PAA content in the hydrogel. The water content increased with increasing pH of the buffer solution. The permeation and release of the drug were tested using indomethacin as a model drug. The permeated and released amounts of the drug increased with decreasing the PAA content because of the low free volume in the hydrogel due to the higher cross-linking density. The kinetic profile of drug release at various pHs showed that all samples reached the equilibrium state within the 5 h.