Manufacturing pharmaceutical products is one of the most regulated industrial processes due to the importance of its effects on human health. These processes require many physical and chemical determinations through chromatographic techniques coupled with different detectors. However, the pharmaceutical industry is not considering the growth that spectroscopic techniques have had in these fields of application, especially to monitor the blending process. This study evaluates different sampling methods for pharmaceutical blending processes by near-infrared spectroscopy (NIRS) and Vis-NIR spectroscopy. The pharmaceutical mixture consisted of three active ingredients at different concentrations. Various qualitative and quantitative strategies were used to evaluate the endpoint of the blending process. The results revealed the feasibility of different spectral analyses to establish the homogeneity of the mixture, which may be especially useful for applications at the industrial level in routine analysis or as a first choice. HPLC confirmed the final blend.