Lithium ephedrates and norcarane-derived lithium amino alkoxides used to effect highly enantioselective 1,2-additions on large scales have been characterized in toluene and tetrahydrofuran. The method of continuous variations in conjunction with Li-6 NMR spectroscopy reveals that the lithium amino alkoxides are tetrameric. In each case, low-temperature Li-6 NMR spectra show stereoisomerically pure homoaggregates displaying resonances consistent with an S-4-symmetric cubic core rather than the alternative D-2d core. These assignments are supported by density functional theory computations and conform to X-ray crystal structures. Slow aggregate exchanges are discussed in the context of amino alkoxides as chiral auxiliaries.