The extraction behavior of DB21C7-HPW synergistic system for Cs has been investigated and compared with that of DB21C7. Two simulated radioactive waste have been examined. It shows that this synergistic system is not only effective for ordinary waste SAW1, but also for the waste of high concentration of nitrates (SAW3). An extraction percentage 99.1% of Cs of SAW3 was obtained by an extracting stage of 5 and scrubbing stage of 3. The stability of synergistic agents towards radiolysis is satisfied and the selectivity for Cs is quite good. Both the additive compound and the extracted Cs complex of DB21C7 and HPW have been separated and identified.