Various elements (Cs, Sr, Ba, Zr, Ru, Pd, Ce, Nd, Gd, Fe, Cr, Ni, Mo and Te) in the simulated high-level radioactive wastes generated from commercial PUREX reprocessing were immobilized by a ceramic solidification using sodium zirconium phosphate, NaZr2(PO4)3 as a host matrix. The convertibility of the elements to the specific M, A and X sites in NZP crystal structure was determined with consideration of stoichiometry, charge balance and ion size of each element. Small disk samples of NZP waste form containing the elements were prepared by the sol-gel synthesis followed by calcination and compression sinteration at high temperature. The physicochemical structures such as produced phase in the waste forms and dispersion of the embedded elements in the NZP waste forms were investigated by means of XRD and SEM/EDX. Chemical behavior of the embedded elements and the limit of substitution of the NZP structure for the elements were investigated by the series of analysis. Moreover, in order to increase the limit of substitution of NZP, the effectiveness of pretreatment with heating the sol-gel products at 473–773K was experimentally investigated. The capability of embedding of NZP for the elements in HLW has been discussed.