Association of enantiopure TRISPHAT anion (1) with chiral spiro [Cu(LL')2] complexes (LL' = 2-R-phen, 2, 6-R-bpy, 3, and 2-iminopyridine, 4) leads to an efficient NMR enantiodifferentiation. Variable temperature 1H NMR spectroscopy has been used to determine the isomerisation kinetics of these pseudo-tetrahedral complexes and to evaluate their configurational stability; the latter depending on the structure of the diimine ligands. In the case of the 2-anthracenyl-phen derivative, a decent level of supramolecular stereocontrol was noted (d.e. up to 45%); the configuration of the complex being determined by electronic circular dichroism (ECD).