Because of its huge economic value, coffee has been the target of adulteration worldwide. Given the successful application of spectroscopic methods in detecting adulterants, this study aimed to employ attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR) to detect adulterants in roasted coffee samples and compare the results with that of sensory analysis. In this study, twelve coffee samples were intentionally adulterated with varying concentrations, i.e., 10%, 30%, and 50%, of corn, beans, sawdust, and coffee husk. These adulterated samples were compared with one unadulterated coffee sample and four roasted and ground commercially available coffee samples; spectral readings of caffeine and chlorogenic acid (CGA) standards were performed for reference. The sensory analysis was performed by 17 tasters who were trained by a Q-grader. The infrared (IR) spectra (FTIR) data were processed by multiplicative signal correction (MSC) and subjected to a principal component analysis (PCA), along with the results of the sensory analysis. The combination of sensory analysis and IR spectrum allowed to differentiate samples of adulterated coffee and unadulterated coffee by PCA, with an explanation of 79% variance. The results demonstrated that the wavenumbers associated with CGA and caffeine contribute significantly in distinguishing adulterated coffee samples.