Using naphthobipyrrole as a functional building block, a new expanded porphyrin; naphthoisoa-, methyrin, was prepared in 85% yield under-acid-catalyzed [4 + 2] MacDonald coupling conditions. Treatment of naphthoisoamethyrin with the nonaqueous uranyl silylamide salt [UO2[N(SiMe3)(2)](2)center dot 2THF] yielded the corresponding uranyl complex. Upon metalation, naphthoisoamethyrin undergoes a two-electron oxidation to yield a formal 22 pi-electron aromatic species, as inferred from H-1 NMR and UV-vis spectrocopy, as well as cyclic voltammetry.