A graphene composite was prepared and coated on the copper wire as extraction fiber.A novel method was developed for the direct measurement of benzene hexachloride（BHC） pesticides residue based on solid phase microextraction（SPME）-gas chromatography equipped with electron capture detection（GC-ECD）.SPME experimental conditions，including extraction time，extraction temperature，pH and ionic strength were optimized.Under the optimized conditions，the self made fiber showed superior extraction efficiencies for α-BHC，β-BHC，γ-BHC and δ-BHC in real water samples with recoveries of 76%-120%.The relative standard deviations（RSDs） of single fiber were in the range of 4.8%-7.5%,and the RSDs between different fibers were 4.1%-9.1%.Good linearities were obtained in the range of 0.5-200 μg/L for four BHCs with detection limits of 0.04-0.15 μg/L.The results indicated that the established method was simple，rapid and sensitive，and was suitable for the determination of benzene hexachloride pesticide residues in water samples.