Strong-aroma Baijiu is a beloved drink in China because of its elegant cellar aroma, sweetness and mellow taste, and its sales account for more than half of the Baijiu production. In this study, three different grades of strong-aroma Baijiu were analyzed systematically using comprehensive two-dimensional gas chromatography–time-of-flight mass spectrometry coupled with molecular sensory science. A total of 342 aroma compounds were identified in the three samples, including 152 aroma-active compounds. Principal component analysis revealed that higher-grade Baijiu contained more terpenes, acetals, and esters. In contrast, lower-grade Baijiu contained fewer esters and many compounds likely generated by the Maillard reaction, such as 5-methylfurfural, 2-propanoylfuran, 2,6-dimethylpyrazine, and 5-ethyl-2(5H)-furanone. Most of the aroma attributes of Baijiu samples could be simulated through aroma recombination experiments, but there were still some slight differences in individual aromas. Finally, the key aroma compounds of the three different grades of Baijiu were revealed through omission experiments. This study provided a scientific basis for the classification of strong-aroma Baijiu quality grades, thereby contributing to the high-quality development of the Baijiu industry.