A binary solvent dispersive liquid-liquid microextraction (BS-DLLME) technique was developed for simultaneous determination of diuron, teflubenzuron, atrazine, and two of its metabolites (desisopropylatrazine and desethylatrazine) in natural waters. The extraction was investigated using a three components mixture design to determine the best ratio between the extractors (dichloromethane and chloroform) and the disperser solvent (acetonitrile). According to the analysis of variance, empirical response surfaces were obtained for each analyte, correlating the absolute recovery and the mixture composition. The analysis of the overlapping surfaces allowed the detection of the best condition for the analytes extraction: 481 µL of chloroform, 56.6 µL of dichloromethane, 906 µL of acetonitrile, 5.00 mL of the aqueous sample, and 10% (m/v) of sodium chloride. The proposed method was validated and successfully applied in the analysis of surface waters, presenting suitable linearity (r > 0.9990), low limits of detection (0.015 to 0.36 µg L -1 ) and quantification (0.049 to 1.2 µg L -1 ), and relative recoveries between 84.8 and 106.1%.