A headspace-solid phase microextraction/gas chromatography-mass spectrometry (HS—SPME/GC—MS) was used to analyze the volatiles of rice contaminated with Aspergillus flavus and their ion chromatograms were obtained. Combined TurboMass and NIST Search software, 26 volatile metabolites were identified in rice contaminated with Aspergillus flavus, including five kinds of aldehydes, six kinds of alcohols, one kind of ketone, nine kinds of hydrocarbons, one kind of ester, one kind heterocyclic, one kind of organic acid, one kind of amine. Based on aflatoxin catabolism and substance transformation in the rice, 2-hydroxy inferred-propionamide and Heptaldehyde are typically volatile component group, which would be used as typical markers to identify rice contaminated by Aspergillus flavus, but also provide a theoretical basis for development of early and rapid detection techniques for identification of contamination rice.