Gem-dihydroperoxides (DHPs), as key intermediates of aldehydes and ketones, are important precursors in synthesis of anti-malaria drugs and have been used as a solid and powerful oxidant in many oxidation organic reactions. For the importance of gem-DHPs, in this work, cesium nitrate has been used as an efficient and commercially available solid catalyst for catalysis peroxidation of aldehydes and ketones to corresponding gem-DHPs by 30% aqueous hydrogen peroxide at room temperature. The reactions carry on with short time and the products were obtained in excellent yields and high purity. In all reaction, no by-product was observed. This methodology is new, easy, effective, and usable.