Wet granulation and direct compression are two processes employed in tablet preparation. In this paper, pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) is used to discriminate these processes with the help of chemometric techniques. The data analysis procedure is as follows. First, deconvolute the Py-GC-MS data of each sample into concentration profiles and spectra, and then construct a matrix with each compound corresponding to one column; those contained only in a small number of samples are then removed. Second, the main principal components are kept after excluding three variables and one sample, and further processed by Fisher discriminant analysis. Third, the resultant data are assigned to classes using unsupervised and supervised classification methods. Results from cross-validation show that only 3 of 20 samples are misclassified by the Mahalanobis distance measure.