Milk is one of the preferred beverages in modern healthy diets, and its freshness is of great significance for product sales and applications. By combining the two-dimensional (2D) correlation spectroscopy technique and chemometrics, a new method based on visible/near-infrared (Vis/NIR) spectroscopy was proposed to discriminate the freshness of milk. To clarify the relationship be-tween the freshness of milk and the spectra, the changes in the physicochemical indicators of milk during storage were analyzed as well as the Vis/NIR spectra and the 2D-Vis/NIR correlation spectra. The threshold-value method, linear discriminant analysis (LDA) method, and support vector machine (SVM) method were used to construct the discriminant models of milk freshness, and the parameters of the SVM-based models were optimized by the grid search method and particle swarm optimization algorithm. The results showed that with the prolongation of storage time, the absorbance of the Vis/NIR spectra of milk gradually increased, and the intensity of autocorrelation peaks and cross peaks in synchronous 2D-Vis/NIR spectra also increased significantly. Compared with the SVM-based models using Vis/NIR spectra, the SVM-based model using 2D-Vis/NIR spectra had a >15% higher prediction accuracy. Under the same conditions, the prediction performances of the SVM-based models were better than those of the threshold-value-based or LDA-based models. In addition, the accuracy rate of the SVM-based model using the synchronous 2D-Vis/NIR autocorrelation spectra was >97%. This work indicates that the 2D-Vis/NIR correlation spectra coupled with chemometrics is a great pattern to rapidly discriminate the freshness of milk, which provides technical support for improving the evaluation system of milk quality and maintaining the safety of milk product quality.