This paper reports on a newly developed elec-trokinetic chromatographic method for the simultaneous separation and determination of steviol glycosides in real stevia samples by capillary electrophoresis and supported by molecular docking studies. Our results obtained using 30-mM heptakis-(2,3,6-tri-o-methyl betacyclodextrin) as a separating agent, suggest that at optimum experimental conditions the detection limits of 2.017 9 10 -5 and 7.386 9 10 -5 M and relative standard deviations (n = 5) of 1.10 and 1.17 were obtained for rebaudioside-A and stevioside, respectively. In addition, the molecular docking studies explained to a certain extent why the separation was successful. The calculated binding free energy results for the rebaudioside-A and stevioside complexes formed with the separating agent showed that although both ligands penetrated deeply into the hydrophobic cavity of the sep-arating agent, the presence of additional hydrogen bonding in the case of stevioside is probably responsible for its stronger binding affinity than that of rebaudioside-A. Keywords Steviol glycosides (rebaudioside-A, stevioside) Á Heptakis 2,3,6-tri-o-methyl betacyclodextrin (TM-b-CD) Á Capillary electrophoresis (CE) Á Molecular docking (MD) Introduction