The first lithium-aziridinylamidinates, Li[(C2H4N)C(NR)2]·THF (R = iPr (3), Cy (4); iPr = isopropyl, Cy = cyclohexyl), have been prepared by addition of N-aziridinyllithium, C2H4NLi (2), to either N,N′-diisopropylcarbodiimide or N,N′-dicyclohexylcarbodiimide. The cyclohexyl derivative 4 was crystallised from both diethyl ether (Et2O) and THF to afford the crystalline solvent adducts {Li[(C2H4N)C(NR)2]·S}2 (4: S = THF; 4a: S = Et2O) which were structurally characterised by X-ray diffraction. In the solid state, these lithium-aziridinylamidinates comprise ladder-type dimeric molecular structures.