An essential oil was distilled with 0.25% yield from fresh flowers of Dalea mutisii Kunth, a native species mainly growing in the Andean region of Ecuador. A total of 50 compounds were identified, and most of them were quantified. The chemical composition was characterized by the prevalence of monoterpene hydrocarbons (>90%). Major components were α-pinene (42.9%), β-pinene (15.1%), β-phellandrene (12.6%), myrcene (6.7%), and (Z)-β-ocimene (5.4%). The essential oil was then submitted to enantioselective analysis, with a 2,3-diethyl-6-tert-butyldimethylsilyl-β-cyclodextrin-based capillary column. An enantiomeric excess was measured for (1R,5R)-(+)-α-pinene (91.6%), (1R,5R)-(+)-β-pinene (15.2%), (R)-(−)-α-phellandrene (4.8%), and (R)-(−)-β-phellandrene (88.8%), whereas (R)-(+)-limonene was enantiomerically pure. A gas chromatography–olfactometry (GC–O) analysis was additionally carried out on this pleasantly fragrant essential oil, following an aroma extract dilution analysis (AEDA) approach. Main odorants were α-pinene, β-pinene, α-phellandrene, and (Z)-β-ocimene, with dilution factors (FD) of 8, 4, 2, and 2, respectively.