Abstract: Pyridine in 15 mL aqueous sample was micro-extracted by using a head space sampling-solid phase microextration system of 75 μm CarboxenTM-Polydimethylsiloxane (CAR-PDMS) fiber. The extractants were measured by Gas Chromatography-Mass Spectrometry (GC-MS) with selected ion monitoring (SIM) mode and internal standard quantitative method. Under the optimum conditions of an extraction temperature of 58.0℃ for 40 min, detection limit, correlation coefficient and linear range were 1.5 μg/L, 0.9994 and 2.5-50.0 μg/L, respectively. The obtained average values of recovery were 75.6%-81.3% (n=6) and the relative standard deviation was 9.60%-12.61% for drinking water samples and pure water with interior spike. Head space sampling-solid phase microextraction (HS-SPME), an organic solvent-free pre-processing method for water sample, can protect SPME coatings, especially for dirty samples. An MS detector has advantages in qualitative analysis and avoids the fake positive signal effect. Head space-solid phase microextraction is a convenient and sensitive method, which is capable of analyzing pyridine in drinking water.