In this paper, the conversion of azoxystrobin in a strongly fluorescent degradation product by UV irradiation with quantitative purposes and its fluorimetric determination are reported for the first time. A multicommuted flow injection-solid phase spectroscopy (FI-SPS) system combined with photochemically-induced fluorescence (PIF) is developed for the determination of azoxystrobin in grapes, must and wine. Grape samples were homogenized and extracted with methanol and further cleaned-up by solid-phase extraction on C 18 silica gel. Wine samples were solid-phase extracted on C 18 sorbent using dichloromethane as eluent. Recoveries of azoxystrobin from spiked grapes (0.5–2.0mgKg −1 ), must (0.5–2.0μgmL −1 ) and wine (0.5–2.0μgmL −1 ) were 84.0–87.6%, 95.5–105.9% and 88.5–111.2%, respectively. The quantification limit for grapes was 0.021mgKg −1 , being within European Union regulations, and 18μgL −1 and 8μgL −1 for must and wine, respectively.