Abstract: GC with headspace-solid phase micro-extraction (HS-SPME) was applied to the determination of pentachlorophenol in human blood. To attain a higher efficiency in SPME, the self-made ionic liquid (IL) bonded coating was selected for the micro-extraction, and the extraction was carried out at 80 ℃ for 50 min. The analyte were separated with HP-5 chromatographic column and detected by FID. Linear relationship between values of peak area and mass concentration of pentachlorophenol was kept in the range of 0.1-100 μg·L-1, with detection limit (3S/N) of 0.01 μg·L-1. Using sample of human blood as matrix, test for recovery was made at 3 concentration levels, values of recovery found were in the range of 89.0%-98.4% with RSD′s (n=8) in the range of 5.8%-8.6%.