Multivariate statistical analysis is applied to geochemical data from three sections forming part of the stratigraphic record of the Cerro Pelado Formation (Oligocene-Miocene), in the central region of the Falcón Basin, northwestern Venezuela. Our main goal is introducing and testing a statistical protocol for the identification of chemofacies in the studied sections. The first step involves data preparation and cleaning: selection of relevant components, convenient replacement of values below the detection limit and determination of outliers. Second, a biplot analysis allows us to infer geochemical processes that can be interpreted from a paleoenvironmental point of view: detrital association, redox-organic matter association and carbonatic association. Considering such geochemical associations, a constrained cluster analysis is then carried out to determine the chemofacies for each section. According to the compositional nature of geochemical data, all statistical analysis is conducted within a log-ratio analysis framework. In addition, robust statistical methods are considered for outlier detection and biplot representation in order to smooth the influence of potential outliers on the estimates.