The Amazon region comprises a plethora of fruit-bearing species of which a large number are still agriculturally unimportant. Because fruit consumption has been attributed to an enhanced physical well-being, interest in the knowledge of the chemical composition of underexplored exotic fruits has increased during recent years. This paper provides a comprehensive identification of the polyphenolic constituents of four underutilized fruits from the Amazon region by HPLC/DAD-ESI-MS(n). Araçá ( Psidium guineense ), jambolão ( Syzygium cumini ), muruci ( Byrsonima crassifolia ), and cutite ( Pouteria macrophylla ) turned out to be primarily good sources of hydrolyzable tannins and/or flavonols. Additionally, different flavanonols and proanthocyanidins were identified in some fruits. The antioxidant capacity was determined by using the total oxidant scavenging capacity (TOSC) assay. Cutite showed the highest antioxidant capacity followed by jambolão, araçá, and muruci.