A low-toxic dispersive liquid-liquid microextraction (DLLME) combined with inductively coupled plasma-MS was used for preconcentration and determination of Cu, Cr, Cd, Ni, Mn, and Pb in real-water samples. In traditional DLLME analysis, chlorinated solvents have been widely used as extraction solvents. However, these solvents are not environmentally friendly. To overcome this problem, we used a low-toxic bromosolvent (1-bromo-3-methylbutane; lethal concentration, 50%, 6150 mg/kg) as the extraction solvent. To study the effects of different parameters on the extraction efficiency, an orthogonal array experimental design with an L16(4(5)) matrix was used. Under the best experimental conditions (i.e., concentration of complexing reagent 1-(2-pyridylazo)-2-naphthol, 1.5 × 10(-3) mol/L; pH, 7.0; volume of acetone, 0.5 mL; volume of 1-bromo-3 methylbutane, 30 μL; and without salt addition), the enhancement factor ranged from 34 to 40. The linear dynamic range was 1-1000 μg/L with r(2) values of 0.9984-0.9999, and the LODs were between 0.042 and 0.53 μg/L. RSDs (at metal ion concentrations of 20 μg/L, n = 6) were 2.12 to 3.42%. The developed method was successfully applied to the extraction and determination of the mentioned metal ions in real-water samples, and satisfactory results were obtained.