In the soil-plant system, the Cr(VI) toxicity can be moderated through redox reactions involving phenolic substances. In such a context, we report the reducing activity of caffeic acid (CAF) towards Cr(VI) in aqueous phase. The redox reaction between Cr(VI) and CAF was studied as a function of both time and pH at different initial metal concentrations. The reaction was particularly effective at pH 2.5. The kinetic data indicate that the reaction proceeds through two steps: the first is faster and involves four electrons, the latter, which is slower, five electrons. The chromatograms evidence the formation of oxidation products (OP) with a different redox activity towards Cr(VI). A yield of Cr(III) equal to that obtained at pH 2.5 and pH 3.1 in about 7 and 25 h, respectively, was reached at pH 4.2 only after a much longer reaction time (50h). At pH>4.2 the reaction occurred even more slowly, and its kinetic trend was more and more difficult to study at pH values higher than 5.0 due to the formation of precipitates. Other phenolics investigated (o-, m-, p-coumaric acids) showed a reducing activity negligible compared to that of CAF: about 30% of p-coumaric acid was oxidized at pH 2.5 only after two months of reaction.