Crystals of [SEt3](3)[Lnl(6)] (Ln = Nd, Sm) were obtained by the reaction of Lnl(2) with the ionic liquid [SEt3][Tf2N] [Tf2N = bis(trifluoromethanesulfonyl)imide]. The compounds are characterized by octahedral [Lnl(6)](3-) units that are surrounded by a distorted cube of triethylsulfonium cations.