A microemulsion electrokinetic chromatography method is described for the simultaneous analysis of local anesthetic drugs, including lidocaine, mepivacaine, bupivacaïne, cinchocaine, cocaine, prilocaine, and ketamine. The effect of the microemulsion composition such as SDS concentration, octane and 1-butanol percentages, as well as the separation temperature, on the electrophoretic behavior of the investigated drugs is described. Results show that the migration window is mainly affected by the SDS concentration in the microemulsion buffer. Adequate separation was performed with an uncoated fused silica capillary (48.5 cm total length x 50 μm ID) and a microemulsion buffer consisting of 50 mM octane, 80 mM sodium dodecyl sulfate, 800 mM 1-butanol, and 10 mM borate buffer (pH 9.0). Retention factors of the investigated anesthetic drugs were highly correlated with the octanol-water partition coefficients. Finally, separation characteristics in MEEKC were compared to those obtained in MEKC under similar micellar conditions. Results indicate the superiority of microemulsion pseudo-phases in terms of selectivity and separation window control.