This review focuses on chemometric techniques applied in MIR-biospectroscopy for cancer diagnosis and analysis over the last ten years of research. Experimental applications of chemometrics coupled with biospectroscopy are discussed throughout this work. The advantages and drawbacks of this association are also highlighted. Chemometric algorithms are evidenced as a powerful tool for cancer diagnosis, classification, and in different matrices. In fact, it is shown how chemometrics can be implemented along all different types of cancer analyses.