The resolution of chiral phenethylamine analogue compounds were studied in presence of single-isomer neutral and negatively charged cyclodextrins (CDs) by means of capillary electrophoresis (CE) and NMR spectroscopy. Whereas the native beta-CD and heptakis(2-N,N-dimethylcarbamoyl)beta-cyclodextrin were not able to separate the racemates of four ephedrine derivatives studied, heptakis(2,3-O-diacetyl)beta-cyclodextrin and especially heptakis(2,3-O-diacetyl-6-sulfo)beta-cyclodextrin could resolve all four pairs of enantiomers in one run. UV and NMR spectroscopic measurements revealed various kinds of complexes of phenethylamines with the CDs. Either defined inclusion complexes or manifold complexes which are mostly characterized by an attachment of the analyte to the outside of the CD cavity were found. No correlation between the kind of complexation and the resolution observed by means of CE could be found.