The present work describes a simple method to detect copper(II) using flame atomic absorption spectrometry (FAAS) after pre-concentration and separation by cloud point extraction(CPE) using N-benzamido-N'-benzoylthiocarbamide (HBBTC) complexing agent and cetyltrimethylammonium bromide (CTAB) as a cationic surfactant. The different experimental parameters such as pH, the concentration of the reagent, centrifuging time, and concentration of CTAB and potassium iodide were examined to increase the extraction efficiency of the proposed procedure. Under optimized extraction conditions the limits of detection and limits of quantification were found to be 0.9 and 2.70 ng mL−1, respectively. The present work was successfully employed for the determination of copper(II) in synthetic mixtures and in water samples with a recovery% greater than 97% and RSD(%) = 0.18 %.