In order to assess the potential of 192 accessions of Capsicum L., from 21 countries, a morphological and agronomic characterization was carried out by applying 57 qualitative and quantitative descriptors. Multivariate analyses identified two large groups: the first including C. annuum (G3, G5, G7 and G8) and the second C. frutescens, C. baccatum, C. chinense and C. pubescens (G1, G2, G4, G6 and G9). The discriminant qualitative descriptors were the colour of the corolla, the colour of the anthers and position of the flower. The quantitative discriminant characteristics were length, weight and width of the fruit. The participatory selection identified 15 materials by colour, aroma, texture, flavour, size and thickness of fruits. Chemical analyses determined the highest concentration of flavonoids in the accessions 10,757 (16.64 mg/g) and 15,661 (15.77 mg/g). Accessions 17,750 (11.68 mg/g) and 10,757 (11.41 mg/g) presented the highest polyphenol contents. The highest capsaicin concentration was recorded in accessions 16,209 (55.90 mg/g) and 10,757 (48.80 mg/g). The highest antioxidant value was recorded in accessions 17,750 (90.85 mg/g) and 15,661 (87.03 mg/g). All these characteristics are important with a view to increasing industrial use and genetic improvement processes. These results show the existence of significant genetic variability within the genus Capsicum.