Baijiu is a traditional and popular Chinese liquor with enormous sale potential, which is affected by factors such as flavor and storage time. Chinese Baijiu is a complex and transparent mixture that makes analyzing difficult. The utility of time-resolved fluorescence helped to develop a new method to analyze Baijiu. Forty-two Baijiu samples among six brands with three flavors were prepared, and their fluorescence spectra were analyzed with an excitation light of 374.2 nm. Hexanoic acid and ethyl butyrate were found to have an impact on Baijiu fluorescence. The properties of lifetimes in Baijiu were investigated, and its mechanism was studied by calculations through density function theory. Using parameters of fluorescence lifetimes, Baijiu samples were classified according to their flavors. Additionally, the correlations between fluorescence lifetimes and storage time of Baijiu in Luzhou flavor were obtained, leading to a reliable and efficient method to establish the year forecast model of Chinese Baijiu with a mean error of 2.79 months. It also provides an important reference of the utility of time-resolved fluorescence for quantitative research of multi-component systems.