Due to fast analysis speed, analyzing composition content of cement raw meal utilizing near infrared (NIR) spectroscopy, combined with partial least squares regression (PLS), is a reliable alternative method for the cement industry to obtain qualified cement products. However, it has hardly been studied. The raw materials employed in different cement plants differ, and the spectral absorption intensity in the NIR range of the raw meal component is weaker than organic substances, although there are obvious absorption peaks, which place high demands on the generality of modeling and accuracy of the analytical model. An effective modeling procedure is proposed, which optimizes the quantitative analytical model from several modeling stages, and two groups of samples with different raw material types and origins are collected to validate it. For the samples in the prediction set from Qufu, the root mean square error of prediction (RMSEP) of CaO, SiO2, Al2O3, and Fe2O3 were 0.1910, 0.2307, 0.0921, and 0.0429, respectively; the average prediction errors for CaO, SiO2, Al2O3, and Fe2O3 were 0.171%, 0.193%, 0.069%, and 0.032%, respectively; for the samples in the prediction set from Linyi, the RMSEP of CaO, SiO2, Al2O3, and Fe2O3 were 0.1995, 0.1267, 0.0336 and 0.0242, respectively, the average prediction errors for CaO, SiO2, Al2O3, and Fe2O3 were 0.154%, 0.100%, 0.022%, and 0.018%, respectively. The standard methods for chemical analysis of cement require that the mean measurement error for CaO, SiO2, Al2O3, and Fe2O3 should be within 0.40%, 0.30%, 0.20%, and 0.15%, respectively. It is obvious that the results of both groups of samples fully satisfied the requirements of raw material proportioning control of the production line, demonstrating that the modeling procedure has excellent generality, the models established have high prediction accuracy, and the NIR spectroscopy combined with the proposed modeling procedure is a rapid and accurate alternative approach for the analysis of cement raw meal composition content.