In the existing study, a new, simple and low cost process for separation/preconcentration of ultra-trace level of inorganic Sb and Se from natural waters, beverages and foods using ultrasonic-assisted cloud point extraction (UA-CPE) prior to their speciation and determination by hydride generation AAS, is proposed. The process is based on charge transfer sensitized complex formations of Sb(III) and Se(IV) with 3-amino-7-dimethylamino-2-methylphenazine hydrochloride (Neutral red, NRH+) in presence of pyrogallol and cetyltrimethylammonium bromide (CTAB) as both sensitivity enhancement and counter ion at pH 6.0. Under the optimized reagent conditions, the calibration curves were highly linear in the ranges of 8-300 ng L-1 and 12-250 ng L-1 (r(2) >= 0.993) for Se(IV) and Sb(III), respectively. The limits of detection were 2.45 and 3.60 ng L-1 with sensitivity enhancement factors of 155 and 120, respectively. The recovery rate was higher than 96% with a relative standard deviation lower than 5.3% for five replicate measurements of 25, 75 and 150 ng L-1 Se(IV) and Sb(III), respectively. The method was validated by analysis of two certified reference materials (CRMs), and was successfully applied to the accurate and reliable speciation and determination of the contents of total Sb/Sb(III), and total Se/Se(IV) after UA-CPE of the pretreated sample matrices with and without pre-reduction with a mixture of L-cysteine and tartaric acid. Their Sb(V) and Se(VI) contents were calculated from the differences between total Sb and Sb(III) and/or total Se and Se(IV) levels. (C) 2016 Elsevier B.V. All rights reserved.