In this paper,we have investigated the formation of the third-phase in tertiary amine(N235)-PtCl62--HCl system and the microscopic phase structural evolution of platinum-loaded organic phases before and after the occurrence of the third-phase.The third-phase is characterized by various spectroscopic techniques,and the small angle X-ray scattering(SAXS) experiments demonstrate the appearance of nano-aggregates,i.e.,water-in-oil reversed micelles,in the third phase.The experimental results indicate that(1) formation of the third phase is related to the aggregation behaviors of nano-reversed micelles in which a super-concentrated hydrochloric acid formed with the H+ to H2O molar ratio being much higher than that of the conventional 37 wt% saturated hydrochloric acid.(2) The occurrence of the super-concentrated HCl results in a great amount of H+ and Cl-ions enriched and confined within the nano-water pools of W/O reversed micelles in third phase.Therefore,the coordination behaviors of platinum complex ions in that super-concentrated hydrochloric acid are very different from their corresponding behaviors in bulk aqueous solutions.It is possible that H+ ions participate in the formation of such complexes as HmPtCl6z+ in the super-concentrated hydrochloric acid.(3) The relative contents of various HmPtCl6z+ complexes are different corresponding to the H+ ion concentrations in confined nanowater pools.The association ability of the acidified tertiary amine N235 molecules(R3NH+) with various HmPtCl6z+ complexes plays an important role in affecting the platinum extraction behaviors. In this paper, we have investigated the formation of the third-phase in tertiary amine (N235) -PtCl62-HCl system and the microscopic phase structural evolution of platinum-loaded organic phases before and after the occurrence of the third-phase. third-phase is characterized by various spectroscopic techniques, and the small angle X-ray scattering (SAXS) experiments demonstrate the appearance of nano-aggregates, ie, water-in-oil reversed micelles, in the third phase. the experimental results indicate that that (1) formation of the third phase is related to the aggregation behaviors of nano-milled micelles in which a super-concentrated hydrochloric acid formed with the H + to H 2 O molar ratio being much higher than that of the conventional 37 wt% saturated hydrochloric acid. (2) The occurrence of the super-concentrated HCl results in a great amount of H + and Cl-ions enriched and confined within the nano-water pools of W / Omicronized micelles in third phase. Beforefore, the coordination behaviors of pla tinum complex ions in that super-concentrated hydrochloric acid are very different from their corresponding behaviors in bulk aqueous solutions. It is possible that that H + ions participate in the formation of such complexes as HmPtCl6z + in the super-concentrated hydrochloric acid. (3) The relative contents of various HmPtCl6z + complexes are different corresponding to the H + ion concentrations in confined nanowater pools. The association ability of the acidified tertiary amine N235 molecules (R3NH +) with various HmPtCl6z + complexes plays an important role in affecting the platinum extraction behaviors.