This paper describes the application of a combined orthogonal array design and overlapping resolution mapping to the optimization of miceller electrokinetic chromatography for the separation of 10 substituted benzenes. The most important factors were first determined according to an OA₁₆(2¹⁵) through 16 pre-designed experiments; a second set of experiments was carried out according to a triangle overlapping resolution mapping scheme, in which 7 pre-planed experiments were executed and global optimum conditions for the separation were obtained.