Separations of enantiomers by capillary electrophoresis (CE) are achieved upon selective interaction of each enantiomer with a chiral selector, resulting in the formation of supramolecular aggregates, or complexes, that may reach the CE detector at different velocities. In order to understand (rationalize) the enantioseparation process and also to be able to modulate its outcome, it is necessary to discern the structure and the stability of these supramolecular complexes. Nuclear magnetic resonance (NMR) constitutes a powerful instrument to elucidate the structure of the complexes at the molecular level. A very important feature of NMR is that the samples to be analyzed can be prepared in a way that mimics the experimental conditions employed in the CE runs, like the pH and composition of the CE conducting medium and the operational temperature. This tutorial describes in detail the necessary steps, from beginning to end, to conduct those NMR experiments to determine the stoichiometry, the values of the association constants, and the 3D structure of the complexes. Precise practical instructions on how to prepare NMR samples from deuterated buffers and stock solutions are given. Other factors influencing the outcome of the NMR analyses, like acquisition parameters of NMR experimental protocols, are also discussed. This chapter pretends to be a concise guide with which researchers with a basic knowledge of NMR can carry out a general and elaborate study into CE-mediated enantioseparations. The stoichiometry and the binding constants of the complexes are determined by titration experiments, whereas 3D structures of the complexes are built upon spotting intermolecular interactions between hydrogen atoms of the analyte and the chiral selector.