A new cloud-point extraction (CPE) for the determination of antimony species in biological and beverages samples has been established with flame atomic absorption spectrometry (FAAS). The method is based on the fact that formation of the competitive ion-pairing complex of Sb(III) and Sb(V) with Victoria Pure Blue BO (VPB+) at pH 10. The antimony species were individually detected by FAAS. Under the optimized conditions, the calibration range for Sb(V) is 1-250 mu g L-1 with a detection limit of 0.25 mu g L-1 and sensitive enhancement factor of 76.3 while the calibration range for Sb(III) is 10-400 mu g L-1 with a detection limit of 5.15 mu g L-1 and sensitive enhancement factor of 48.3. The precision as a relative standard deviation is in range of 0.24-235%. The method was successfully applied to the speciative determination of antimony species in the samples. The validation was verified by analysis of certified reference materials (CRMs). (C) 2014 Elsevier Ltd. All rights reserved.