During the last decade several research groups have been developing electrochemical procedures to access highly functionalized organic molecules. Among the most exciting advances, the possibility of using free radical chemistry has attracted the attention of the most important synthetic groups. Nowadays, electrochemical strategies based on these species with a synthetic purpose are published continuously in scientific journals, increasing the alternatives for the synthetic organic chemistry laboratories. Free radicals can be obtained in organic electrochemical reactions; thus, this review reassembles the last decade's (2010–2020) efforts of the electrosynthetic community to generate and take advantage of the C‐, O‐, and N‐centered radicals’ reactivity. The electrochemical reactions that occur, as well as the proposed mechanism, are discussed, trying to give clear information about the used conditions and reactivity of these reactive intermediate species.
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