Hydrogen peroxide (H2O2) is encapsulated in silica hydrogels using sol‐gel method and the effects of the K+ : Na+ ion ratio on gelation time, hydrogel structure, stability, and release rate of H2O2 were investigated. As the amount of K+ ions increased relative to the amount of Na+ ions at the same pH, the gel structure became less compact and the pore diameter increased. Hydrogen peroxide retention values up to 90 and 80% were observed at the end of 7 and 20 days, respectively, in the presence of K+ ions at low pH values when the initial H2O2 concentration was 19.9 wt %. Release rate of hydrogen peroxide decreased with decreasing pH for the two K+ : Na+ ion ratios studied. This work presents an environmentally friendly, low cost, and easy to scale up method to increase the stability of high initial concentrations of H2O2 at room temperature and customize the release rate. © 2016 American Institute of Chemical Engineers AIChE J, 63: 409–417, 2017