Volatile compounds in coffee were determined by gas chromatography-mass spectrometry (GC-MS) combined with headspace solid phase microextraction (HS-SPME) using a GC capillary column of HP-5MS (30 m x 0.25 mm x 0.25 μm) and the following suitable HS-SPME conditions: temperature of 90 ° C, extraction time of 45 min and desorption time of 5 min. Comparing with the NIST library database, 72 volatile compounds were identified, along with eight major components with normalized peak area above 1% such as 2-methoxy-4-vinylphenol, 2-furanmethanol, furfural, pyridine, furfuryl acetate, 5-methyl-2-furancarboxaldehyde, 2-methyl-pyrimidine and 2-furanyl-1-ethanone. Using chemometrics with principal components analysis (PCA) of 45 selected volatile compounds, coffee samples from four geographical origins (Chiangmai, Chiangrai, Krabi, Chumphon) were classified with different PCA patterns. This indicates that HS-SPME/GC-MS combined with chemometrics can be used an alternative method for identification of coffee from different geographical origins.