N,β-D-glucopyranosyl vincosamide (GPV), a major alkaloid of Psychotria leiocarpa, constitutes up to 2.5% of the dry weight in leaves. Alkaloid content was not elicited by mechanical wounding or jasmonate. At concentrations found in natural conditions or 2.5 fold higher, GPV did not inhibit herbivory in two unrelated generalist models (Helix aspersa and Spodoptera frugiperda) or in a specific interaction model (Heliconius erato fed with Passiflora suberosa). In situ staining assay showed quenching activity of hydrogen peroxide by GPV. Exposure of P. leiocarpa to acute UV-B stress did not change GPV or chlorophyll content, indicating high tolerance to this stress by the species. In vitro antioxidant tests against singlet oxygen, superoxide anions and hydroxyl radicals showed efficient quenching activity of the alkaloid. GPV was not effective as antifeedant, but it may act indirectly in P. leiocarpa protection against oxidative stress generated upon wounding, UV exposure and perhaps other environmental stresses.