The feasibility of the discrimination of Chinese rice wines with respect to their geographic origin and wine age using volatile profiles and chemometric methods was investigated. Stir bar sorptive extraction with thermal desorption and gas chromatography-mass spectrometry (SBSE-TD-GC-MS) was used for the determination of volatile compounds. A total of 63 volatile compounds were identified, including 30 esters, 9 alcohols, 9 aldehydes, 7 acids, 4 ketones, 3 volatile phenols and 1 miscellaneous compound. The major compounds in Chinese rice wine were ethanol, isoamyl formate, ethyl acetate, diethyl succinate, phenylethyl alcohol, benzaldehyde, ethyl lactate, 2-butanol and ethyl butyrate. Principal component analysis (PCA) and cluster analysis (CA) were used to characterize the different Chinese rice wine samples by geographic origin and wine age. The PCA results showed that the characterization of Chinese rice wine by SBSE-TD-GC-MS was highly related to geographic origin and wine age. The CA results indicated that geographic origin had more of an effect than wine age on the character of Chinese rice wine, and that 5-year old wines had a transition of flavor. The results showed that SBSE-TD-GC-MS together with chemometric methods could provide a practical reference for the characterization of Chinese rice wines.