Motivated by the culinary and ethnopharmacological use of Acmella oleracea (L.) R.K. Jansen, this study aimed to unveil new chemical compounds from its essential oil (EO). Acmella oleracea , known for its anesthetic and spicy properties, has been used in traditional medicine and cuisine, particularly in Northern Brazil. Through a detailed GC-MS analysis, 180 constituents were identified, including 12 tentatively identified long-chain α-keto esters of various acids. Additionally, 18 new esters were synthesized for structural verification. This research expands the known chemical diversity of A. oleracea EO, providing a basis for potential pharmacological applications. The identification of new natural products, including homologs and analogs of acmellonate, underscores the EO's rich chemical profile and its potential for novel bioproduct development.