The determination of Pb(II) and Cd(II) in different sample matrices, including drinking water, distilled spirits and fruit wine, was carried out by flame atomic absorption spectrometry (FAAS) after pre-concentration using homogeneous liquid-liquid extraction (HLLE). First, the HLLE method was optimised with lead diethyldithiocarbamate (Pb-DDTC) complex which was extracted with a perfluorooctanoate anion (PFOA -) dissolved in lithium hydroxide under acidic conditions. The optimum extraction conditions, using 0.01 M DDTC, 0.05 M PFOA -, 3 M HCl and 1 mL of 30 vol. % acetone, were obtained. The Pb-DDTC complex in the nitric acid digest of the samples (50-150 mL) was extracted quantitatively into a drop of 100 Β΅L of sediment phase. The sediment phase dissolved in 1 vol. % HNO3 with at least 3-5 mL of the final volume was then determined by FAAS, affording a pre-concentration factor of 10-50. Hence, the HLLE method afforded an increase in both sensitivity and selectivity for the metal determination by conventional FAAS, resulting in ultra-trace level detection of Pb(II) in all samples analysed (drinking water, 9.2-23 ng mL -1 ; distilled spirits, 23-50 ng mL -1 ; fruit wine, 24-53 ng mL -1 ). In addition, the proposed method could successfully be applied to Cd(II) determination in these samples.