Herein, a chemophenetic significance, based on phenolic metabolite profiling of three Senecio (S. hercynicus, S. ovatus and S. rupestris) and two Jacobaea species (J. pancicii and J. maritima) coupled to morphometric data, is presented. A set of twelve morphometric characters were recorded from each plant species and used as predictor variables in a Linear Discriminant Analysis (LDA) model. From a total 75 observations (15 from each of the five species), the model correctly assumed their species' membership, except 2 observations. Among the studied species, S. hercynicus and S. ovatus presented the greatest morphological similarity. A phytochemical profiling of phenolic specialized metabolites by UHPLC-Orbitrap-HRMS revealed 46 hydroxybenzoic, hydroxycinnamic, acylquinic acids and their derivatives, 1 coumarin, and 21 flavonoids. Hierarchical and PCA clustering applied to the phytochemical data corroborated the similarity of S. hercynicus and S. ovatus, observed in the morphometric analysis. This study contributes to the phylogenetic relationships between the tribe Senecioneae taxa and highlights the chemophenetic similarity/dissmilarity of the studied species belonging to Senecio and Jacobaea genera.