Since the chemical analysis advancement has required increasingly chemometric applications, teaching materials became important for the infrared spectrometry teaching. In this sense, it is proposed an experimental activity for undergraduate and graduate students, where hierarchical cluster analysis (HCA) and principal component analysis (PCA) are applied in infrared spectra of organic solvents. Four studies were accomplished in a gradual manner, starting with the analysis of the simplest groups to the most complex group. The procedure analysis of the hydrocarbon, alcohols and ketones samples effectively illustrated the concepts of multivariate exploratory analysis, HCA and PCA. In addition, the resulting spectra clearly demonstrated the differences of the organic functions and aromaticity and also the used software proved to be adequate for users with little prior knowledge in this area.