In order to achieve rapid, non‐destructive, efficient, and accurate classification of paper cup samples, we propose a classification model that integrates shifted‐excitation Raman difference spectroscopy (SERDS) with self‐organizing map (SOM) and Bayesian optimization–support vector machine (BO‐SVM). We collected differential Raman data from 52 paper cup samples using SERDS, with an excitation wavelength range of 784–785 nm, a laser power of 440 mW, an integration time of 10 s, and a spectral range spanning from 280 to 2700 cm−1. Subsequently, principal component analysis (PCA) was applied to reduce the dimensionality of the data. The SOM clustering outcomes were utilized as the foundation for constructing the discriminant analysis (FDA) and BO‐SVM classification models. The primary constituent of the paper cup samples was identified as cellulose, while additional fillers such as talc, calcium carbonate, and kaolin were also present. The SOM clustering categorized the samples into seven distinct groups. The FDA model achieved a classification accuracy of 92.3%, and the BO‐SVM model reached a classification accuracy of 96.2%. The SOM clustering effectively discerned samples with different fillers, as evidenced by distinct peak numbers and shapes in the differential Raman spectra, thereby underscoring the practical significance of SOM clustering. In comparison with FDA, BO‐SVM exhibited enhanced classification accuracy and exceptional performance in handling outliers and linearly inseparable data, indicating its superior generalization capabilities.