To determine the key odorants of a popular Chinses rice wine, Shaoxing-jiu, volatile compounds were analyzed by using sensory-directed flavor approaches, including gas chromatography-mass spectrometry (GC-MS), gas chromatography-flame photometric detector (FPD), gas chromatography olfactometry (GC-O), aroma recombination and omission experiments, and odorant addition experiments. Fifty-five volatile compounds were detected in traditional Shaoxing-jiu via GC-MS, more than those in mechanical Shaoxing-jiu. Thirty-four aroma-active compounds in traditional Shaoxing-jiu were determined via GC-O. According to aroma recombination and omission experiments, the aroma profile of the recombination model constructed by these aroma-active compounds at their detected concentrations was similar to that of traditional Shaoxing-jiu, and 15 of them were affirmed as key odorants. Among the key odorants, phenylethyl alcohol, furfural, γ-nonalactone and dimethyl trisulfide presented very highly significant aroma contributions, indicating that their omission would cause great aroma differences. Then odorant addition experiments highlighted the aroma impacts of these four paramount key odorants on sensory descriptors in traditional Shaoxing-jiu.