This paper contains data on the chemical composition of the essential oils of 22 leaf samples of Piper marginatum Jacq. collected in different areas and ecosystems of the brazilian Amazon, as well as an overview of the available literature. The species presents a large synonymy based on their different leaf characteristics and distinct scents where some of them smell like anise or very close compounds. By GC, GC/MS, and cluster analysis, we identified seven chemotypes for the leaf oils. The main components found in chemotype I were safrole (1) and 3,4-(methylenedioxy)propiophenone (2). The chemotype II was dominated by 3,4-(methylenedioxy)propiophenone (2) and p-mentha-1(7),8-diene (10). The major compounds identified in chemotype III were 3,4-(methylenedioxy)propiophenone (2), myristicin (3), (E)-beta-ocimene (11), and gamma-terpinene (12). In the chemotype IV, the principal constituents were beta-caryophyllene (13), alpha-copaene (14), and 3,4-(methylenedioxy)propiophenone (2). The chemotype V was dominated by (E)-isoosmorhizole (6), (E)-anethole (8), and isoosmorhizole (7). The main compounds found in the chemotype VI were 2-methoxy-4,5-(methylenedioxy)propiophenone (4), methoxy-4,5-(methylenedioxy)propiophenone isomer 5, and (E)-isoosmorhizole (6). The major constituents in chemotype VII were beta-caryophyllene (13), bicyclogermacrene (15), and (E)-asarone (9).