Natural phenolic compounds are abundant in the vegetable kingdom, occurring mainly as secondary metabolites in a wide variety of chemical structures. Around 10,000 different plant phenolic derivatives have been isolated and identified. This review provides an exhaustive overview concerning the electron transfer reactions in natural polyphenols, from the point of view of their in vitro antioxidant and/or pro‐oxidant mode of action, as well as their identification in highly complex matrixes, for example, fruits, vegetables, wine, food supplements, relevant for food quality control, nutrition, and health research. The accurate assessment of polyphenols’ redox behavior is essential, and the application of the electrochemical methods in routine quality control of natural products and foods, where the polyphenols antioxidant activity needs to be quantified in vitro , is of the utmost importance. The phenol moiety oxidation pathways and the effect of substituents and experimental conditions on their electrochemical behavior will be reviewed. The fundamental principles concerning the redox behavior of natural polyphenols, specifically flavonoids and other benzopyran derivatives, phenolic acids and ester derivatives, quinones, lignins, tannins, lignans, essential oils, stilbenes, curcuminoids, and chalcones, will be described. The final sections will focus on the electroanalysis of phenolic antioxidants in natural products and the electroanalytical evaluation of in vitro total antioxidant capacity.