The third-phase formation behavior in ionic liquid (IL) extraction system using trioctylphosphine oxide (TOPO) was investigated. In the use of a relatively less-lipophilic IL, such as 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (CmimTfN), the third phase was formed between the aqueous phase and the IL phase. The third phase seems to have a relatively high lipophilicity compared to the IL phase. The main components of the third phase were suggested as being (HO)TOPO, IL anion (TfN), IL cation (Cmim) and free TOPO. In addition, the third phase showed an extraction concentration ability for the Fe(III)-thiocyanato complex.