A cyclic epicatechin trimer with C3 symmetry, connected through C−C bonds between A‐ and B‐rings, was isolated as an oxidative coupling product of (−)‐epicatechin with polyphenol oxidase. It was previously isolated as an oxidation product of epicatechin with CuCl2; however, only the 2D structure was proposed. Its stereochemistry was assigned using various spectroscopic techniques, including 1D and 2D NMR, and theoretical calculations of the NMR and ECD data. It was suggested that the less strained cyclic trimer with the (aR,aR,aR) configuration was formed atroposelectively in the cyclization process.