The aggregation states of partially saponified [di-(1-methylheptyl) phosphoric acid] (DMHPA)-tributyl phosphate (TBP) heptane (C7H16) and the extracted organic phases containing rare earth were studied. The result demonstrates that TBP can widen the range of the microemulsion formation in DMHPA-C7H16-NaOH-H2O systems. It also influence the states of the extracted organic phases of DMHPA-RE (III) and the behavior of water clearly. The gel could be formed in DMHPA-TBP-RE (III) systems under proper conditions. FT-IR spectra analysis shows that both DMHPA and TBP may coordinate with RE3+ and the hydrogen bonds of TBP with DMHPA and H2O contribute to the three dimensional network structure of the gels.