The aroma profile of Chinese rice wine was investigated in this study. The volatile compounds in a traditional Chinese rice wine were extracted using Lichrolut EN and further separated by silica gel normal phase chromatography. Seventy-three aroma-active compounds were identified by gas chromatography-olfactometry (GC-O) and gas chromatography-mass spectrometry (GC-MS). In addition to acids, esters, and alcohols, benzaldehyde, vanillin, geosmin, and γ-nonalactone were identified to be potentially important to Chinse rice wine. The concentration of these aroma-active compounds in the Chinese rice wine was further quantitated by combination of four different methods, including headsapce-gas chromatography, solid phase microextraction-gas chromatography (SPME)-GC-MS, solid-phase extraction-GC-MS, and SPME-GC-pulsed flame photometric detection (PFPD). Quantitative results showed that 34 aroma compounds were at concentrations higher than their corresponding odor thresholds. On the basis of the odor activity values (OAVs), vanillin, dimethyl trisulfide, β-phenylethyl alcohol, guaiacol, geosmin, and benzaldehyde could be responsible for the unique aroma of Chinese rice wine. An aroma reconstitution model prepared by mixing 34 aroma compounds with OAVs > 1 in an odorless Chinese rice wine matrix showed a good similarity to the aroma of the original Chinese rice wine.