jats:titleAbstract</jats:title>jats:pA redox‐switchable self‐assembled Znjats:supII</jats:sup>jats:sub4</jats:sub>Ljats:sub6</jats:sub> cage was synthesized that contains naphthalenediimide (NDI) motifs. Its reduction lent these NDI panels persistent radical anion character. The redox activity of this cage allows it to act as a catalyst for the oxidative coupling of different tetraaryl borates to give biaryls. The catalytic activity of the cage was enhanced following its binding of Cjats:sub60</jats:sub>, which implies a mechanism that does not involve encapsulation of the substrate.</jats:p>