The aim of this work is to solve the practical problem that there are relatively few fast, intelligent, and objective methods to distinguish dairy products and to further improve the quality control methods of them. Therefore, an approach of cheese product brand discrimination method based on Raman spectroscopy and probabilistic neural network algorithm was developed. The experimental results show that the spectrum contains abundant molecular vibration information of carbohydrates, fats, proteins, and other components, and the Raman spectral data collection time of a single sample is only 100 s. Due to the high spectral similarity between samples, it is impossible to identify them with naked eyes. Characteristic peak intensity combined with statistical process control method was employed to study the fluctuation characteristics of samples. The results show that the characteristic peak of experimental samples fluctuates within a certain control limit. However, due to the high similarity between the Raman spectra of different brand samples, they cannot be effectively identified as well. This paper further studied and established the analytical approach based on Raman spectroscopy, including wavelet denoising, normalization, principal component analysis, and probabilistic neural network discrimination. In db1 wavelet processing, [−1, 1] normalization, 74 principal components (cumulative contribution rate of 100%) can realize the effective discrimination of different brands of cheese products in 1 s, with the average recognition accuracy of 96%. The discriminant method established in this work has the advantages of simple operation, rapid analysis, and accurate results. It provides a technical reference for the fight against counterfeit products and has a broad application prospect.