The extraction behavior of five rare earth ions (RE3+) was investigated in ionic liquid (IL) extraction system using 1-butyl-3-methyl-imidazolium hexafluorophosphate ionic liquid ([Bmim]PF6) as extraction solvent and benzoyl acetone (HA) as extractant. The extraction percentage of RE3+ using [Bmim]PF6 was less than 8% without HA. When sufficient HA was included in IL phase, the extraction percentage of RE3+ could be higher than 98%. The extracted species in the RE3+-[Bmim]PF6-HA system was neutral REA3 and the recovery of RE3+ extracted into [Bmim]PF6 can be achieved using the mixture of hydrazine hydrate and ethylenediamine tetraacetic acid (EDTA) as stripping agent. [Bmim]PF6 can be recycled in the experiment.