Objective: This study aimed to optimize the aging technology of Fuyuxiangxing crude Baijiu and improve its quality. Methods: Testing and analyzing the new wine and the Fuyuxiangxing crude Baijiu aged for 1, 3, 5, 8 and 10 years allowed for the analysis of the physicochemical indexes such as pH, conductivity, viscosity, total acid and total ester. Additionally, the primary volatile flavor components of the six samples were qualitatively assessed using GC and GC-MS, and 26 volatile flavor components of the samples were quantitatively assessed using the external standard method. Results: With the increase of aging time, the conductivity increased, the viscosity increased, the total acid content increased and the total ester content decreased; 26 volatile flavor components were quantified in the 6 Fuyuxiangxing crude Baijiu, including 8 esters, 8 alcohols, 5 acids and 5 aldehydes and ketones, with the contents of esters increasing and then decreasing, the contents of alcohols showing a slow decreasing trend, and the contents of acids and aldehydes increasing. Both the principal component analysis (PCA) and the partial least squares discriminant analysis(PLS-DA) could better distinguish Fuyuxiangxing crude Baijiu with different aging time. Conclusion: The preliminary study reveals the changing rules of physicochemical properties and flavor substances during the aging process of Fuyuxiangxing crude Baijiu, and the appropriate aging time can improve the quality of crude Baijiu, which can provide a reference for the optimization of the aging technology of Fuyuxiangxing crude Baijiu.