A method for the determination of trace Te in the complex geological samples by hydride generation atomic fluorescence spectrometry using MIBK as extraction reagent was developed. The extraction ability of Te(Ⅳ) in the HCl-NaBr-MIBK system and the anti-extraction behavior of Te(Ⅳ) in the HCl-KMnO4-MIBK system were studied. Under the optimum extraction condition of 3.6 mol·L-1 HCl-100 g·L-1 NaBr, Te(Ⅳ) was extracted completely by MIBK, Te(Ⅳ) in the MIBK phase was oxidized to Te(Ⅵ) with HCl-KMnO4, Te(Ⅵ) in the MIBK phase was anti-extracted using water, then the interference elements such as Au, Ag, Pt, Pd, Cu, Pb, Co, Ni, Cd, As, Sb, Bi, Hg, Tl and Se for the determination of Te by hydride generation atomic fluorescence spectrometry were eliminated successfully. The detection limit of Te was 1.14 10-4 μg·g-1, and the relative standard deviations of Te was 6.84%. The method was applied to complicated geological samples.