The aim of this work was the two‐aqueous phase extraction of neutral red and methylene blue from wastewater. This has been achieved on the basis of phase separation properties of non‐ionic surfactants above the so‐called cloud point curve and the solubilization phenomena of coacervate micelles (surfactant rich phase). Three commercial surfactants were used in this work; the Oxo‐C15E7 which is an ethoxylate fatty alcohol (Dehydol LT 7), Triton X‐114 (iso‐C8H17‐C6H4‐(OCH2CH2)7,5OH), and Triton X‐100 (iso‐C8H17‐C6H4‐(OCH2CH2)9,5OH) which are alkyl phenol ethoxylate surfactants. The phase diagrams of binary water/surfactants systems were drawn and the effect of sodium sulphate on water‐surfactant systems was therefore studied. Oxo‐C15E7 and Triton X‐114 were used for the cloud point extraction of neutral red and methylene blue from their aqueous solutions at 100 mg/L and 7 mg/L, respectively. The experimental extraction results were expressed by the following three responses: percentage of the extracted dye (E), residual concentrations of dye in the dilute phase (Xs,w), and the volume fraction of coacervate (φC) at the equilibrium. The results obtained for each parameter were also represented on three‐dimensional diagrams using an empirical smoothing method. The empirical modelling data were in agreement with the experimental ones. The main advantage was sought between E, which has reached 99% in the case of neutral red, whereas in the case of mehtylene blue 92% was obtained with respect to (φC), which should have a minimum value. At the optimal conditions, neutral red and methylene blue concentrations in the effluent were reduced to about 500 times and 7 times, respectively.