Mass spectrometry has become the preferred analytical technique to characterize organic compounds in biological samples because of its sensitivity and selectivity. Hybrid UHPLC coupled to Orbitrap mass analyzer is an innovative state of the art technology that allows fast and accurate metabolomic analyses. In this work, Several flavanones, flavonols, and benzoic acid geranyl derivatives were rapidly identified in the resinous exudate of Heliotropium taltalense Phil., an endemic species growing in Paposo valley northern Chile, by means of ultrahigh resolution liquid chromatography Orbitrap MS-MS analysis (UHPLC-PDA-OT-MS). The relationship between the compounds detected and some biosynthetic pathways or mechanisms of formation of the geranyl derivatives are proposed. Furthermore, some common flavonoids and the new compound 3,4-dihydroxy-5-geranyl-benzoic acid were isolated from the plant resin using liquid-liquid high speed countercurrent chromatography (HPCCC). The new structure was elucidated by spectroscopic means (NMR).