The first simultaneous use of a chiral surfactant and a chiral oil for microemulsion EKC (MEEKC) is reported. Six stereochemical combinations of dodecoxycarbonylvaline (DDCV: R, S, or racemic, 2.00% w/v), racemic 2-hexanol (1.65% v/v), and dibutyl tartrate (D, L, or racemic, 1.23% v/v) were examined as chiral pseudostationary phases (PSPs) for the separation of six pairs of pharmaceutical enantiomers: pseudoephedrine, ephedrine, N-methyl ephedrine, metoprolol, synephrine, and atenolol. Subtle differences were observed for three chromatographic figures of merit (alpha(enant), alpha(meth), k) among the chiral microemulsions; a moderate difference was observed for efficiency (N) and elution range. Dual-chirality microemulsions provided both the largest and smallest enantioselectivities, due to small positive and negative synergies between the chiral microemulsion components. For the ephedrine family of compounds, dual-chiral microemulsions with surfactant and oil in opposite stereochemical configurations provided higher enantioselectivities than the single-chiral component microemulsion (RXX), whereas dual-chiral microemulsions with surfactant and oil in the same stereochemical configurations provided lower enantioselectivities than RXX. Slight to moderate enantioselective synergies were confirmed using a thermodynamic model. Efficiencies observed with microemulsions comprised of racemic dibutyl tartrate or dibutyl-D-tartrate were significantly higher than those obtained with dibutyl-L-tartrate, with an average difference in plate count of about 25 000. Finally, one two-chiral-component microemulsion (RXS) provided significantly better resolution than the remaining one- and two-chiral-component microemulsions for the ephedrine-based compounds, but only slightly better or equivalent resolution for non-ephedrine compounds.