Résumé : A reversed-phase high-performance liquid chromatographic (HPLC) procedure for the determination of chlordiazepoxide, its four metabolites and three unstable photoproducts (oxaziridines) generated by UV irradiation is reported. The influence of pH and acetonitrile (CH3CN) and tetrahydrofuran (THF) percentages in the mobile phase was investigated. The optimum method uses a Nucleosil C18 column (5 μm) with a mobile phase consisting of CH3CN-THF-0.06 M phosphate buffer (pH 5.8) (22:2:76). Eight drugs covering a wide range of lipophilicity and polarity were separated in 50 min. The absolute detection and quantification limits of benzodiazepines were less than 1 and 5 ng, respectively. The HPLC method alone or coupled with the UV irradiation procedure showed good precision (R.S.D. 1.7-4.0%) and excellent linearity in the range of 1.5-43 μg/ml (r ≥ 0.999).