A robust general route to lanthanide dicyanamide (DCA(-)) complexes has been developed where f-element salts are dissolved in DCA(-)-based ionic liquids (ILs) directly or formed in situ, forcing coordination of these normally weakly coordinating soft N-donor anions, even in an ambient, non-moisture-excluding environment. A series of lanthanide complexes [C(2)mim][Ln(DCA)(4)(H2O)(4)] (C(2)mim = 1-ethyl-3-methylimidazolium; Ln = La, Nd, Eu, Tb, Dy, and Yb) and [C(2)mim](3n)[La(OH2)(4) (mu(2)-DCA)(4)](n)[La(OH2)(2)(mu(3)-DCA)(3)(mu(2)-DCA)(4)](2n)(Cl)(4n) were crystallized under a variety of conditions using this methodology and structurally characterized using single crystal X-ray diffraction. Although not all examples were isostructural, the dominant feature across the series was the presence of [Ln(DCA)(4)(H2O)(4)](-) anionic nodes with all terminal DCA(-) ligands accepting hydrogen bonds from the coordinated water molecules forming a 3D metal organic framework. To determine if any structural clues might aid in the further development of the synthetic methodology, the metal-free IL [C(1)mim][DCA] (C(1)mim = 1,3-dimethylimidazolium), a room-temperature solid, crystalline analogue of the reaction IL, which is liquid at room temperature, was also prepared and structurally characterized. The ready isolation of these compounds allowed us to begin an investigation of the physical properties such as the luminescence at room and low temperatures for the Eu, Tb, and Dy representatives.