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Determination of 135Cs concentration and 135Cs/137Cs atomic ratio is of great importance in characterization of radioactive waste from decommissioning of nuclear facilities. In this work, an effective analytical method was developed for simultaneously determination of 135Cs and 137Cs in different types of waste samples (steel, zirconium alloy, reactor coolant, ion exchange filter paper and spent ion exchange resin) by coupling AMP-PAN, AG MP-1M and AG 50 W-X8 chromatographic separation with ICP-MS/MS measurement. Decontamination factors of 7.0 × 106 for Co,