Objective： The purpose of this study was to explore the contribution of Hongqu and Baiqu to the formation of volatile flavors in Hongqu rice wine. Method： Headspace solid-phase microextraction-GC/ MS， principal component analysis （PCA）， and orthogonal partial least squares discriminant analysis （OPLS-DA） were used to screen out the volatile flavor compounds with significant difference among the rice wines brewed using different starters. Result： There were 10 volatile flavor compounds with significant difference between A wine （brewed using Hongqu + Baiqu） and B wine （brewed using Hongqu）. There were 8 volatile flavor compounds with significant difference between A wine （brewed using Hongqu + Baiqu） and C wine （brewed using Baiqu）， 8 volatile flavor compounds with significant difference between B wine （brewed using Hongqu） and C wine （brewed using Baiqu）. Conclusion： It can be deduced that the contribution of Hongqu to the formation of volatile flavors of Hongqu rice wine was the most significant， while the influence of white koji on the formation of volatile flavor compounds in Hongqu rice wine was relatively weak.