A study on the selective separation of $^{99}Tc,\;^{94}Nb,\;^{55}Fe,\;^{90}Sr$ and $^{59}Ni(^{63}Ni)$ from various radioactive wastes discharged from the nuclear power plants in Korea is being performed for use in their quantifications which are indispensible for the evaluation of the radionuclide inventory. Separation behaviour of Ce, Ca, Mg, Al, Cr, Ti, Mn and Cu recovered along with Ni during the separation of Re (as a surrogate of $^{99}Tc$), Nb, Fe and Sr by anion exchange and Sr-Spec extraction chromatography was investigated by cation exchange and Ni-Spec extraction chromatography using synthetic radioactive waste dissolved solutions containing matrix elements such as Re, Nb, Fe, Sr, Ni, B, Na, K, Ce, Co, Ca, Mg, Al, Zn, Cr, Pb, Cd, Mo, Mn, Cu, Zr, Ti and U. To purify the Ni fraction recovered and prepare a radionuclide source available for gas proportional counting, an application of the Ni precipitation procedure with dimethylglyoxime in the medium of ammonium citrate and tartaric acid solutions as a masking agent for co-existing metal ions was described in detail.