A simple and selective micellar electrokinetic chromatographic (MEKC) method has been developed for the analysis of five pharmaceutical binary mixtures containing three non-steroidal anti-inflammatory drugs (NSAIDs). The investigated mixtures were Ibuprofen (IP)–Paracetamol (PC), Ibuprofen (IP)–Chlorzoxazone (CZ), Ibuprofen (IP)–Methocarbamol (MC), Ketoprofen (KP)– Chlorzoxazone (CZ) and Diclofenac sodium (DS)–Lidocaine hydrochloride (LC). The separation was run for all mixtures using borate buffer (20 mM, pH 9) containing 15% (v/v) methanol and 100 mM sodium dodecyl sulphate (SDS) at 15 kV and the components were detected at 214 nm. Different factors affecting the electrophoretic mobility of the seven investigated drugs were studied and optimized. The method was validated according to international conference of harmonization (ICH) guidelines and United States pharmacopoeia (USP). The method was applied to the analysis of five pharmaceutical binary mixtures in their dosage forms. The results were compared with other reported high performance liquid chromatographic methods and no significant differences were observed.