Phosphorite is a nonrenewable strategic resource, a convenient and rapid method of phosphorite grade identification and classification is important to improve phosphate utilization. In this study, Raman spectroscopy has been combined with principal component analysis and hierarchical clustering analysis (PCA-HCA) and orthogonal partial least squares-discriminant analysis (OPLS-DA) models for an investigation of different grade phosphorite samples. Both the PCA-HCA and OPLS-DA models showed that different grade phosphorite samples can be clearly distinguished by statistically analyzing the Raman spectra after smoothing, baseline correction, and first derivation. In addition, the S-line study on the OPLS-DA model clearly demonstrated that the symmetrical stretching vibrational mode of phosphate near 960 cm−1 had a much more significant contribution than other vibrational modes for the differentiation of different grade phosphorite samples.