Extraction behaviour of trivalent americium and europium was investigated with 1-phenyl-3-methyl-4-acetyl-5-pyrazolone (HPMAP) and tri-n-octylphosphine oxide (TOPO) in a room-temperature ionic liquid, 1-methyl-3-octyl-imidazolium bis(trifluoromethylsulphonyl) imide (C(8)mimTf(2)N). In select cases, comparison was made using xylene, a molecular diluent. For binary extraction studies involving only PMAP, Eu3+ was marginally better extracted than Am3+ and the species extracted into C(8)mimTf(2)N conformed to species of the type M(PMAP)(3) (where M = Am or Eu). On the other hand, cationic species were extracted for the ternary extraction systems involving HPMAP and TOPO. Luminescence spectroscopic studies suggested no inner-sphere water molecules in the extracted species. The luminescence decay lifetime showed mono-exponentials, suggesting the extraction of single species.