Abstract: GC with headspace-solid phase micro-extraction (HS-SPME) was applied to the determination of tetraethyl lead in water. To attain a higher efficiency in SPME, the PDMS fiber was selected as coating for the micro-extraction, and the extraction was carried out at 60 ℃ for 30 min. The analyte were separated on DB-5 chromatography column and detected by ECD. Linear relationship between values of peak area and mass concentration of tetraethyl lead was kept in the range of 0.05-20.0 μg·L-1, with detection limit (3S/N) of 0.02 μg·L-1. Using water sample as matrix, test for recovery was made by addition of standard solution at 3 concentration levels, values of recovery found were in the range of 87.0%-90.1% with RSD′s (n=7) in the range of 3.7%-4.2%.