Species of the Annonaceae family are used in traditional medicine, and several antitumor acetogenins have been isolated from the leaves of Annona muricata and Rollinia mucosa. Leaves samples (self-shaded and sun-exposed) of these species were collected during winter and summer seasons. Extraction media were prepared from mixtures of five solvents according to a simplex centroid design. Plant extracts were analysed by injection into a high-performance liquid chromatography with diode array detection (HPLC-DAD) and evaluated after applying by multivariate curve resolution-alternating least-squares (MCR-ALS) and discriminant-unfolded partial least-squares (D-UPLS). The objective was to check whether the chemometric resolution of chromatographic profiles could help in the discrimination of samples according to taxonomic classification, sun exposition and/or harvest season. The results indicate that extraction media containing ethanol as main solvent achieved discrimination of self-shaded versus sun-exposed plants and harvest season of Annona muricata. Also, D-UPLS analysis allowed taxonomic discrimination between Annona muricata and Rollinia mucosa extract samples.Fil: Afonso, Sabrina. Universidade Estadual de Londrina. Departamento de Química. Laboratório de Quimiometria em Ciências Naturais; Brasil.Fil: Silva, Fabiano. Universidade Estadual de Londrina. Departamento de Química. Laboratório de Quimiometria em Ciências Naturais; Brasil.Fil: Scaminio, Ieda. Universidade Estadual de Londrina. Departamento de Química. Laboratório de Quimiometria em Ciências Naturais; Brasil.Fil: Pisano, Pablo Luis. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Departamento de Química Analítica; Argentina.Fil: Olivieri, Alejandro César. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Departamento de Química Analítica; Argentina.