New ion exchanger with porous silica as a supporting material and diphosphonic acid as a functional chelating group has been developed for the effective removal of transition metals and actinide ions from radioactive liquid wastes ranging from neutral to very acidic conditions. Thermal treatments of metal (Co, Cs or U) loaded resin after sol-gel reaction with various additives were performed to investigate the possibility of enhancing the physicohcemical characteristics and converting the powder waste into a monolithic final waste form. Experimental results showed that addition of Ti could increase the binding force between nuclides and solidification matrix. Moreover, monolithic ceramic waste forms could be easily fabricated by using a hot press unit even at a relatively lower temperature than that of vitrification process.