A simple and effective hollow fiber based-liquid phase microextraction (HF-LPME) technique by using ionic liquid, 1-hexyl-3-methylimidazolium hexafluorophosphate, [C6MIM][PF6], coupled with electrothermal atomic absorption spectrometry (ETAAS) was developed for the determination of lead and nickel in environmental and biological samples. Ammonium pyrroldinedithiocarbamate (APDC) was used as chelating agent. Several factors that influence the microextraction efficiency and ETAAS signal, such as pH, APDC concentration extraction time, amounts of ionic liquid, stirring rate, pyrolysis and atomization temperature were investigated and the microextraction conditions were established. In the optimum experimental conditions, the detection limits (3 s) of the method were 0.03 and 0.02 mu g L-1, for Ni and Pb, respectively and corresponding relative standard deviations (0.5 mu g L-1, n=6) were 4.2% and 5%. The developed method was validated by the analysis of certified reference materials and applied to the determination of lead and nickel in real samples. (C) 2009 Elsevier B.V. All rights reserved.