Nowadays, coffee, cocoa, and spices have broad applications in the food and pharmaceutical industries due to their organoleptic and nutraceutical properties, which have turned them into products of great commercial demand. Consequently, these products are susceptible to fraud and adulteration, especially those sold at high prices, such as saffron, vanilla, and turmeric. This situation represents a major problem for industries and consumers’ health. Implementing analytical techniques, i.e., Fourier transform mid-infrared (FT-MIR) spectroscopy coupled with multivariate analysis, can ensure the authenticity and quality of these products since these provide unique information on food matrices. The present review addresses FT-MIR spectroscopy and multivariate analysis application on coffee, cocoa, and spices authentication and quality control, revealing their potential use and elucidating areas of opportunity for future research.