A simple, rapid and efficient dispersive liquid–liquid microextraction based on the solidification of floating organic drop (DLLME–SFO) method, followed by inductively coupled plasma-optical emission spectrometry (ICP-OES) was developed for the simultaneous preconcentration and determination of heavy metals in water samples. One variable at a time method was applied to select the type of extraction and disperser solvents. Then, an orthogonal array design (OAD) with OA 16 (4 5 ) matrix was employed to study the effects of different parameters on the extraction efficiency. Under the best experimental conditions (extraction solvent: 140μL of 1-undecanol; disperser solvent: 2.0mL of acetone; ligand to metal mole ratio: 20; pH: 6 and without salt addition), the enhancement factor ranged from 57 to 96. The calibration graphs were linear in the range of 0.5–250μgL −1 for Mn, 1.25–250μgL −1 for Cr, Co and Cu with correlation coefficient (r) better than 0.990. The detection limits were between 0.1 and 0.3μgL −1 . Finally, the developed method was successfully applied to extraction and determination of the mentioned metal ions in the tap, sea and mineral water samples and satisfactory results were obtained.