In order to detect the age of aged Baijiu quickly and accurately, 3-D fluorescence spectra of aged Baijiu and base wine were analyzed by parallel factor algorithm and spectral similarity algorithm. The determination functions of volume fraction of high age base wine and age determination functions of aged Baijiu were established respectively. The results show that the determination error of volume fraction of high age base wine did not exceed 0.02, the average spiked recovery was 100.28%, and the error of age determination was less than 1 year; the method based on 3-D fluorescence spectra for rapid determination of age of aged Baijiu solved the difficulty of age identification due to the complexity of 3-D fluorescence spectra of 3 base wine formulations of aged Baijiu. This study provides a reference for the problem of age detection of aged Baijiu formulated with multiple base wines and the determination of the volume fraction of base wine among aged Baijiu.