This study reports a simple, rapid and greener method based on ultrasound assisted-cloud point extraction coupled with inductively coupled plasma-optical emission spectroscopy (ICP-OES) for preconcentration and determination of antimony (Sb), tin (Sn) and thallium (Tl) in food and water samples. Factors affecting the preconcentration procedure were optimized using fractional factorial design and response surface methodology based on Box-Behnken design. Under optimum conditions, the calibration graphs were linear over the concentration range of 0.023–700 μg L−1 with correlation coefficients up to 0.9994, the limits of detection ranged from 0.007–0.010 μg L−1, the limits of quantification were from 0.023 to 0.033 μg L−1 and the relative standard deviations (n = 15) were between 1.3% and 4.1%. In addition, the preconcentration factors were found to be 150, 145 and 160 for Sb, Sn and Tl, respectively. Finally, the developed method was successfully applied in various food and water samples as well as certified reference materials for rapid determination of Sb, Sn and Tl.