Four different chiral diamino ðers synthesized from N-isopropyl valinol or N-isopropyl alaninol were lithiated with n-butyllithium in tetrahydrofiiran or diethyl ether. Crystal structures of the dilithiated diamino diethers were determined by X-ray diffraction. Three dilithiated diamino diethers including (2S,2'S)-1,1'-(butane-1,4-diylbis(oxy))bis(N-isopropylpropan-2-amine) 7, (2S,2'S)-1,1'-(pentane-1,5-diyIbis(oxy))bis(N-isopropylpropan-2-amine) 8, and (2S,2 'S) -1,1 ' - (heptane-1,7-diylbis( oxy))bis (N-isopropyl-3methylbutan-2-amine) 9 are dimers, whereas dilithiated (2S,2 'S) -1,1 ' - (pentane-1,5-diyIbis (oxy))bis (N-isop ropyl -3methylbutan-2-amine) 10 is a monomer. The lithium atoms in all crystal structures adopt a nonequivalent coordination protocol and exist in two different environments in which one of the lithium atoms is tetra-coordinated while the other one is tri-coordinated. The solution structures of the dilithiated diamino diethers are also characterized by a variety of NMR experiments including diffusion-ordered NMR spectroscopy (DOSY) with diffusion coefficient-formula (D-FW) weight correlation analyses and other one- and two-dimensional NMR techniques.