The volatile constituents of Michelia alba flowers, including fresh flowers, frozen flowers and withered flowers, were investigated by GC–MS. The volatiles in a simulated natural environment were sampled by solid-phase microextraction (SPME), with a 100 μm polydimethylsiloxane fiber at 25±5°C for 4 h. The fibers were desorbed in a GC injection liner at 250°C for 3 min. With headspace SPME–GC–MS analysis, 61 peaks were separated. The main compounds in headspace of fresh Michelia alba flowers included α-myrcene, ( S)-limonene, ( R)-fenchone, linalool, camphor, caryophyllene, germacrene D, etc., a greater number of compounds than for frozen flowers and withered flowers. At the same time, the biomarkers of fresh flowers were compared with the frozen flowers and withered flowers. In this study, headspace SPME–GC–MS afforded a simple and more sensitive sampling method for fresh Michelia alba flowers and other fresh flowers.