Guarana [Paullinia cupana var. sorbilis (Mart.) Ducke] is a typical South American plant, native to the Amazon, with subspontaneous occurrence in Maués, Amazonas, Brazil, where it was domesticated and cultivated by the Sateré‐Mawé indigenous community. Guarana is an original Brazilian product with great economic and industrial potential owing to the energetic, antioxidant, and medicinal properties of its seeds. In spite of its importance, there is still a gap in knowledge about genetic diversity and adaptations that might improve agro‐industrial uses of guarana seeds. This study was aimed at estimating phytochemical diversity, classification, and typology of guarana genotypes. Agro‐industrial potential among eight genotypes was estimated based on phytochemical characters (theobromine, caffeine, catechin, and epicatechin content, quantified by high performance liquid chromatography) and yield in three locations from harvests between 2015 and 2016. Phytochemical divergence was assessed by the mean Euclidean distance. Grouping was performed by the unweighted pair‐group method using arithmetic averages. Metabolite content varied considerably between genotypes (e.g., among caffeine [3.23–7.35%], catechin [0.20–3.57%], and epicatechin [0.09–4.22%]), and dry seed yield was the character with the greatest variation (0.048–5.13 kg plant−1). The metabolic profile variations of the genotypes were clustered into three chemotypes: energetic and antioxidant guarana (genotypes CIR815, CIR904, and CMA498); antioxidant guarana (genotypes BRS‐Maués and CMU874); and energetic guarana (genotypes CMA831, CMU952, and BRS‐CG372). Genotypes CIR815, CIR904, and CMU874 have the potential to be future commercial cultivars, providing quality raw material for soft drinks, energy drinks, and pharmaceutical products.