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Different chemiluminescence systems based on luminol, permanganate, manganese(IV) and cerium(IV) reagents were compared regarding their sensitivity and selectivity to determine plant polyphenols. Among the seventeen systems tested, Mn(IV)-formaldehyde-hexametaphosphate was considered to be the most suitable for polyphenols detection. The developed flow injection method (FI-CL) based on enhancing effect of polyphenols on Mn(IV) chemiluminescence is characterised by low detection limit of gallic acid (0.02 μg L−1) and high precision (RSD = 1.7%). The calibration graph was linear from 0.1 to 100 μg L−1. The selectivity studies revealed that the FI-CL method ensures accurate determination of the total polyphenols content in food samples. The method was successfully applied to analysis of a variety of plant-derived foods (wine, tea, cereal coffee, fruit and vegetable juices, herbs and spices). The proposed method is superior to conventional spectrophotometric assays due to its higher sample throughput (195 samples h−1), simplicity, sensitivity and, above all, higher selectivity.