A hydrogen‐bonded complex was successfully isolated as crystals from the anthranol/anthroxyl pair in the self‐exchange proton‐coupled electron transfer (PCET) reaction. The anthroxyl radical was stabilized by the introduction of a 9‐anthryl group at the carbon atom at the 10‐position. The hydrogen‐bonded complex with anthranol self‐assembled by π–π stacking to form a one‐dimensional chain in the crystal. The conformation around the hydrogen bond was similar to that of the theoretically predicted PCET activated complex of the phenol/phenoxyl pair. X‐ray crystal analyses revealed the self‐exchange of a hydrogen atom via the hydrogen bond, indicating the activation of the self‐exchange PCET reaction between anthranol and anthroxyl. Magnetic measurements revealed that magnetic ordering inside the one‐dimensional chain caused the inactivation of the self‐exchange reaction.