By gelation with sodium silicate and phosphorous oxide in binary system, we investigated the possibility to fix the volatile alkali metal chlorides in a highly stable matrix at high temperature if the product gel is further solidified to form glass or ceramic waste form. The binary system with different metal chloride (MCI) loadings underwent gelation reaction at 70 ℃ for 1 day and dried at 110 ℃ for 1 day. XRD analysis showed that all the dried gel contained NaCl and some unknown crystalline phase. From the experimental results, the reaction mechanism can be proposed as follows. Also, the possibility of Cs vaporization could be lowered by the application of the new gel-route stabilization/solidification to treat waste salt. (G, Na) + MCl → (G, M) + NaCl, (G, H) + MCl → (G, M) + HCl.