A specific, accurate, precise and reproducible micellar electrokinetic chromatographic method was developed for in vitro and in vivo estimation of rosuvastatin, a synthetic and potent HMG-CoA inhibitor, in rabbit plasma. Further, its pharmacokinetics in the presence of niacin, which could be co-administered for monitoring of severe hypercholestremia, was investigated. The assay procedures involved simple liquid-liquid extraction of rosuvastatin and internal standard, atorvastatin, from a small plasma volume directly into acetonitrile. The organic layer was separated and evaporated under a gentle stream of nitrogen. The residue was reconstituted in the mobile phase and injected electrokinetically into electropherosis system. The background electrolyte consisted of borate buffer (25.0 mm, pH 9.5), 10.0% organic modifier (5.0% methanol + 5.0% acetonitrile) and 25.0 mm sodium dodecyl sulfate at 20.0 kV applied voltage and 215.0 nm detection wavelength for the effective separation of rosuvastatin, niacin and atorvastatin.