To explore the effects of pH on properties of polyvinyl alcohol (PVA)-ionic hydrogels containing wound healing promoters. PVA was combined with a natural wound healing promoter (silk sericin (SS)), and an anionic agent (eosin (ES)) or cationic agent (methylene blue (MB)), and made into hydrogels. Properties of the hydrogels and behaviour at different pHs were investigated. The density and gel fraction of PVA/SS-ES hydrogel and PVA/SS-MB hydrogel were considerably lower compared with hydrogel without SS. The swelling ratio and degradation of the hydrogels increased with increasing SS concentration in all pH solutions. The influence of SS in interrupting long-chain PVA molecules was confirmed based on changes in Fourier-transform infrared spectroscopy (FTIR). The SS released from the gels was found to interact with the ionic agent and influenced the release profile of the ionic agent. Surprisingly, the anionic agent in PVA/SS-ES hydrogel showed 70% release in high pH solution whereas the cationic agent in PVA/SS-MB hydrogel showed 86% release in low pH solution. Moreover, the active agent could accumulate on the skin layer and had a positive effect on a specific wound area. Based on the results obtained in this study, it is suggested to use anionic hydrogels containing wound healing promoter for wounds at high pH and cationic hydrogels containing wound healing promoter for wounds with low pH. Ability to improve wound healing using a natural healing agent combined with ionic agents and controlling the pH of hydrogels will help in developing quick and low-cost treatment for wounds.