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Floral and fruity aromas are vital indicators for evaluating the quality of the sauce-flavored Baijiu, however, are hard to analyze and elucidate due to the interference of other aromas in the liquor. Herein, we developed a pervaporation membrane separation technology (PV), that effectively reduces the complexity of analyzing floral and fruity aromas and enables the identification of key flavor compounds of the floral and fruity aromas in sauce-flavored Baijiu. Contributed to the separation via PV on flavor, liquor samples differing in floral and fruity aromas are efficiently separated that allows to be sensitively analyzed by gas chromatography-ion mobility spectrometry (GC-IMS) and gas chromatography-mass spectrometry (GC-MS). We found that a total of 29 compounds that potentially contributed to floral and fruity aroma. Aroma recombination and omission/addition experiments were conducted to verify the contribution of these compounds to the overall aroma, leading to the identification of 15 key aroma compounds including affecting floral and fruity aromas. And discovered esters serving as key components for contributing floral and fruity aromas. Meanwhile, Acetals can make the aromas become more coordinated and aldehydes facilitate floral and fruity aroma release. The work contributes to a tool for elucidating complexity of flavor compounds in Baijiu.