In this review, we have focused mainly on the study of their antioxidant and pro-oxidant capacity, and the analysis of the oxidation of the catechol group to o-quinone. The redox balance established between the different oxidase and reductase enzymes generates reducing species, H+ and e−, and allows the oxidation of polyphenolic groups to quinones to be reversible. This continuous balance between these nucleophilic and electrophilic substances allows the activation of the NRF2/ARE axis, which regulates cellular antioxidant responses against oxidative stress, as well as cell proliferation. Understanding the ambivalent character of polyphenols, which can act simultaneously as antioxidants and pro-oxidants, will allow the design of specific therapies that can serve science and medicine in their tasks.