Abstract: In order to quickly determine the volume fraction of acetic acid in Chinese aged liquor, 3-D fluorescence spectroscopy and alternate fitting residual algorithm were used. Firstly, 3-D fluorescence spectra of different volume fraction of acetic acid of ethanol aqueous solution was used as the calibration set. 3-D fluorescence spectrum of liquor was used as the predicted set. Alternate fitting residual algorithm was used to analyze. Standard addition method was used to verify the accuracy of the results. Through theoretical analysis and experimental verification, the results show that, correlation coefficient between the predicted volume fraction and the experimental volume fraction is 0.9926. Average recovery percentage is 101.97%. 3-D fluorescence spectrometry combined with alternate fitting residual algorithm can quickly and effectively determine the volume fraction of acetic acid in Chinese aged liquor. This result is helpful for the detection of monomer volume fraction in Chinese aged liquor.