Abstract: The unsaponified P204-H3cit-NdCl3 extraction system can effectively solve the pollution problem of the saponification waste water in traditional Nd extraction separation systems. But further application of this method is limited by high acidity of the re-extraction process in this system.The effect on re-extraction ratio of re-extraction acidity, temperature, times, and stage was investigated through single-level re-extraction and cross-flow re-extractions. With these results as a foundation, further studies were conducted for countercurrent re-extraction with low acidity of 0.6mol/L and six stages. Results indicated that countercurrent re-extraction rate reached 100% compared to single-stage and cross-flow re-extraction, and acid consumption was significantly reduced to 50%. Acidity remaining after re-extraction was 0.3 mol/L, and this meets the industrical requirements of the rare earth extraction. These methods of unsaponified P204-H3cit-NdCl3 extraction provided a certain basis for the application of rare earth elements.