In consideration of the world's present environmental situation and the threat of species extinction, investigations concerning alternative sustainable sources of natural substances represent an extremely important issue. In this respect, the present research is focused on the analytical evaluation of Brazilian rosewood (Aniba rosaeodora Ducke) leaves, as an alternative source (with respect to wood) of rosewood essential oil and, as such, of natural linalool, which is extensively used in perfumery. Enantioselective-gas chromatography-olfactometry (Es-GC-O) was used as a tool for the simultaneous stereodifferentiation and olfactive evaluation of the volatile optically active components present in the analyzed samples. In addition to Es-GC-O analyses, direct olfactive analyses were also performed, enabling the evaluation of the global aroma exerted by each sample and the influence of each linalool antipode, as also other minor compounds. The samples were also submitted to gas chromatography-mass spectrometric analysis, thus establishing their chemical profiles. The assessment of enantiopure chiral compounds through Es-GC-O, along with direct olfactive analyses, confirmed that the leaves are a potential substituent for wood in the extraction of Brazilian rosewood essential oil, representing a sustainable nonwood source of natural linalool.