In this work, a new method based on dispersive liquid–liquid microextraction (DLLME) preconcentration using tetrachloromethane (CCl₄) as extraction solvent was proposed for the spectrophotometric determination of cadmium and copper in water and food samples. The influence factors relevant to DLLME, such as type and volume of extractant and disperser solvent, concentration of chelating reagents, pH, salt effect, were optimized. Under the optimal conditions, the limits of detection for cadmium and copper were 0.01ng/L and 0.5μg/L, with enhancement factors (EFs) of 3458 and 10, respectively. The tremendous contrast of EFs could come from the different maximum absorption wavelength caused by the different extraction acidity compared with some conventional works and the enhancement effect of acetone used as dilution solvent during the spectrophotometric determination. The proposed method was applied to the determination of water and food samples with satisfactory analytical results. The proposed method was simple, rapid, cost-efficient and sensitive, especially for the detection of cadmium.