► A new method was developed to determine inorganic Se species by CPE–FAAS. ► A method for determination of selenium using CPE/FAAS system has not been published previously. ► The proposed method is fairly simple, cheap, environmental friendly and useful. ► The linear range of the method is highly wide and suitable for its application to real food samples. A useful preconcentration and determination method was proposed for trace selenium in food samples. The procedure is based on complex formation of Pyronine B with Se(IV) ions in the presence of sodium dodecyl sulphate (SDS) and Ponpe 7.5. The variables affecting complex formation, extraction and phase separation were studied and optimised. Under the experimental conditions used, the calibration graph was linear in the range of 20–1700μgL−1 for Se(IV) ions. The limit of detection was 3.81μgL−1 of Se(IV) and the relative standard deviation for 5 replicate determinations at 250μgL−1concentration level was 2.45%. Recovery values were obtained between 97.8% and 102.8% for spiked samples. The method was successfully applied to the determination of total selenium in some food samples and alcoholic and nonalcoholic beverages. Its validity was checked by the analysis of four certified reference materials. The results obtained by the proposed method were quantitatively in good agreement with the certified values.