We established pretreatment method of solidified cement ion-exchange resin samples generated before 2003 in nuclear power plants for measurement of non-volatile radionuclide activity. A microwave digestion system (MDS) with mixed acid (HCl-HNO3-HF-H2O2) was used to dissolve cement and to desorb non-volatile elements such as Ce, Co, Cs, Fe, Nb, Ni, Re, Sr and U from mixed ion-exchange resin. The content of Ce, Co, Fe, Nb, Ni, Re, Sr, U and Cs after pretreatment of cement plus mixed ion-exchange resin was measured by ICP-AES and ICP-MS, respectively. As iron and strontium are also present in cement, their content after dissolving a certain amount of cement was measured by ICP-AES. All elements except Nb were quantitatively recovered. Especially since the Nb recovery was low at 72.0±2.5%, the MDS following addition of the mixed acid to the resin was operated once more for desorbing Nb from it. Finally the recovery of Nb was over 95%. This sample pretreatment method will be applied to solidified cement ion-exchange resin samples generated in nuclear power plants for assessment of radionuclide inventory.