Ionogels are solid oxide host networks confining at a meso-scale ionic liquids, and retaining their liquid
nature. Ionogels were obtained by dissolving anthanide(III) complexes in the ionic liquid 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C6mim][Tf2N], followed by confinement of the lanthanide-doped ionic liquid mixtures in the pores of a nano-porous silica network. [C6mim][Ln(tta)4], where tta is 2-thenoyltrifluoroacetonate and Ln = Nd, Sm, Eu, Ho, Er, Yb, and [choline]3[Tb(dpa)3], where dpa = pyridine-2,6-dicarboxylate (dipicolinate), were chosen as the lanthanide complexes. The ionogels are luminescent, ion-conductive inorganic–organic hybrid
materials. Depending on the lanthanide(III) ion, emission in the visible or the near-infrared regions of the electromagnetic spectrum was observed. The work presented herein highlights that the confinement did not disturb the first coordination sphere of the lanthanide ions and also showed the excellent luminescence performance of the lanthanide tetrakis b-diketonate complexes. The crystal structures of the complexes [C6mim][Yb(tta)4] and [choline]3[Tb(dpa)3] are reported.