The volatile and semi-volatile compounds of Chinese rice wines were extracted by headspace solid phase microextraction (HS-SPME) and analyzed by gas chromatography-mass spectrum (GC-MS). The original Chinese rice wine samples were diluted with deionized water to a final concentration of 6% (v/v) ethanol and then extracted by HS-SPME. The samples were pre-equilibrated at 50°C for 15 min and extracted with stirring at the same temperature for 45 min prior to injection into a GC-MS. A total of 97 volatile and semi-volatile compounds were identified from ten Chinese typical rice wine samples, including 13 alcohols, 8 acids, 28 esters, 4 aldehydes and ketones, 17 aromatic compounds, 3 lactones, 6 phenols, 3 sulphides, 9 furans and 6 nitrogen-containing compounds, of which, 39 compounds were firstly reported in Chinese rice wine. By stepwise linear discrimination analysis, the ten Chinese rice wine samples could be classified into three groups according to the production area, and in particular, the production technologies.