On the basis of Li-7 NMR measurements, we have made detailed studies on the influence of the ionic liquids [emim] [NTf2], [emim][ClO4], and [emim][EtSO4] on the complexalion of Li+ by the bidentate N-donor ligands 2,2'-bipyridine (bipy) and 1,10-phenanthroline (phen). For each of the employed ionic liquids the NMR data implicate the formation of [Li(bipy)(2)](+) and [Li(phen)(2)](+), respectively. X-ray diffraction studies were performed to determine the coordination pattern in the solid state. In the case of [emim] [ClO4] and [emim][EtSO4], crystal structures confirmed the NMR data, resulting in the complexes [Li(bipy)(2)ClO4] and [Li(phen)(2)EtSO4], respectively. On the contrary, the ionic liquid [emim][NTf2] generated the C, symmetric, dinuclear, supramolecular cluster [Li(bipy)(NTf2)](2), where the individual Li+ centers were found to be bridged by two [NTf2] anions. Density functional theory (DFT)-calculations lead to further information on the effect of stacking on the coordination geometry of the Li+ centers.