The content of Na+, RE3+ and the swelling characteristic of dried gel containing DMHPA[di-(1-methylheptyl)phosphoric acid]-RE(III) have been studied by FTIR and ICP/AES spectroscopy methods. The result demonstrates that (1) the mechanism of microemulsion extracting lanthanide ions is complicated and it is difficult to be explained with simple chemical equations, (2) The dried gel can swell, but the aggregation states and microstructure change as the used solvents and its content vary, (3) The far infrared spectroscopy shows that there are ring structures in the gel and differences of the ability in coordination with DMHPA between light and heavy lanthanide ions.