(4NPEA)(2)PbI4 (4NPEA = 4-nitrophenylethylammonium) is the first 3 X 3 corrugated 2D organic-Pb/I perovskite. The nitro groups are involved in cation-cation and cation-iodide interactions. The structure contains both highly distorted and near-ideal PbI6 octahedra, consistent with the observation of two Pb-207 NMR resonances, while the optical properties resemble those of other 2D perovskites with distorted PbI6 octahedra.