The comparative metabolic profiling and their biological properties of eight extracts obtained from diverse parts (leaves, flowers, roots) of the medicinal plant Flourensia fiebrigii S.F. Blake, a chemotype growing in highland areas (2750 m a.s.l.) of northwest Argentina, were investigated. The extracts were analysed by GC‐MS and UHPLC‐MS/MS. GC‐MS analysis revealed the presence of encecalin (relative content: 24.86%) in ethereal flower extract (EF) and this benzopyran (5.93%) together sitosterol (11.35%) in the bioactive ethereal leaf exudate (ELE). By UHPLC‐MS/MS the main compounds identified in both samples were: limocitrin, (22.31%), (2Z)‐4,6‐dihydroxy‐2‐[(4‐hydroxy‐3,5‐dimethoxyphenyl)methylidene]‐1‐benzofuran‐3‐one (21.31%), isobavachin (14.47%), naringenin, (13.50%), and sternbin, (12.49%). Phytocomplexes derived from aerial parts exhibited significant activity against biofilm production of Pseudomonas aeruginosa and Staphylococcus aureus, reaching inhibitions of 74.7–99.9% with ELE (50 µg/mL). Notably, the extracts did not affect nutraceutical and environmental bacteria, suggesting a selective activity. ELE also showed the highest reactive species scavenging ability. This study provides valuable insights into the potential applications of this chemotype.