• The differential accumulation of various polyphenols, particularly of flavonoids and hydroxycinnamates, was studied in leaves of Ligustrum vulgare exposed to increasing sunlight under well watered or drought-stress conditions. • Light- and drought-induced changes in leaf polyphenol concentrations were normalized to the CO₂ assimilation rate. The functional roles of flavonoids and hydroxycinnamates were analysed through tissue localization using multispectral fluorescence microimaging, and through efficiencies to scavenge superoxide radicals (O₂⁻) and to screen UV wavelengths. • Clear effects of light and water treatments on leaf polyphenol concentrations were not observed, as the CO₂ assimilation rate varied according to sunlight and water availability. However, biosynthesis of quercetin 3-O-rutinoside, luteolin 7-O-glucoside and echinacoside, which were efficient O₂⁻ scavengers, increased sharply in response to solar radiation. By contrast, carbon for the synthesis of p-coumaric acid and monohydroxyflavones, efficient UV screeners but poor O₂⁻ scavengers, did not vary depending on light treatments. Flavonoids accumulated in both the adaxial epidermis and the palisade tissue because of sunlight irradiance, whereas echinacoside occurred largely in abaxial tissues. • We hypothesize that flavonoids may serve antioxidant functions in response to excess light and drought stress, and that a coordinate control system between hydroxycinnamate and flavonoid pathways operated in L. vulgare exposed to excess light.