A method has been investigated for high-speed and efficient recovery of palladium from reprocessing waste of spent nuclear fuel by mixing the matrix feedstock with a small amount of KI and an appropriate inert solvent (such as kerosene) as collecting agent. Equilibrium of the reaction can be obtained in less than 30 sec. Percent recovery of palladium is more than 97%. Decontamination coefficient is high. No loss of effectiveness of the system was observed below 1×106 rad of irradiation.