Nevirapine (11-cyclopropyl-4-methyl-5,11-dihydro-6H-dipyrido[3,2-b:2',3'-e][1,4]diazepin-6-one)1,2 is a non-nucleoside reverse transcriptase inhibitor (NNRTI) that stops HIV from multiplying by preventing the reverse transcriptase enzyme from working. This drug is usually included in the generic fixed-dose combinations and has shown efficacy in advanced HIV disease.3 Several analytical methods have been developed for analyzing nevirapine and other antiretroviral drugs including derivative UV spectrophotometry4 and high performance thin layer chromatography (HPTLC).5 High performance liquid chromatography (HPLC) has been widely used for determination of antiretrovirals in both biological fluids and pharmaceutical formulations,6-11 hyphenated HPLC-MS12-17 systems have also been introduced for the determination of antiretrovirals in plasma. Many of these methods require the use of expensive and hazardous chemicals which make the process complex, time consuming and costly. Capillary electrophoresis has become an active research and development area of considerable interest in analytical chemistry and has been widely adopted for the analysis of drugs and pharmaceuticals18 due to its simplicity, wide application, small sample volume requirement, short analysis time, high resolution and low running cost with eco-friendly solvents as compared to HPLC.