The invention discloses an analytical method for identifying a flavor characteristic index compound of chilli oil. The quality of chilli oil is determined by qualitative and quantitative analysis. Through a headspace solid-phase microextraction technology and a gas chromatography-mass spectrometry coupling technology, volatile components that contribute to the aroma in chili oil can be analyzed and quantitatively detected. The good products and defective products obtained by judgment are analyzed to obtain the qualitative and quantitative changes of the volatile components, and the characteristic substances of chili oil and the content range thereof are found out. When the volatile substances of chili oil are in this range, the chilli oil is a good product, otherwise the chilli oil is a defective product. The method has the advantages of high accuracy and small error, and is favorable to the stable control of chilli quality.