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A new member of the cyclo[n]pyrrole class of expanded porphyrins was prepared from the corresponding thiophene-containing terpyrrole precursor through use of a mild electrochemical oxidative procedure. The isolated macrocycle, featuring nine heterocyclic subunits directly connected through their α,α′-positions, is the largest cyclo[n]pyrrole derivative reported to date. The structure obtained via synchrotron radiation-based studies revealed a dimeric arrangement involving individual macrocyclic subunits.