A method based on headspace solid-phase microextraction (HS-SPME) coupled with gas chromatography-mass spectrometry (GC-MS) was used for the analysis of volatile compounds in “Hengshui Laobaigan” liquor. Five different fibers were evaluated in terms of the number of volatile compounds, sensitivity and reproducibility. The results showed that 50/30 μm divinylbenzene/carboxen/polydimethylsiloxane (DVB/CAR/PDMS) fiber was most suitable for acquiring a complete profile of the volatile compounds in Laobaigan liquor. For specific applications, 75 μm carboxen/polydimethylsiloxane (CAR/PDMS) fiber was appropriate to extract acids, alcohols, pyrazines and aromatic and phenolic compounds because of its high sensitivity, and 50/30 μm DVB/CAR/PDMS fiber was found to have higher sensitivity than others for extracting esters, hydrocarbons, aldehydes and ketones. It is concluded that different fibers should be selected depending on different research objects for acquiring accurate and reliable results.