Reaction of [Zn-II(TTP)] (1) (TTP = dianion of 5,10,15,20-meso-tetrakis(p-tolypporphyrin) with 16 equiv of N-bromosuccinamide (NBS) in methanol at reflux led to the unexpected two-sidedd open-ring brominated product [Zn-II(C26H20N2O2Br5)(2)] (2). Similar observations have been made with other meso-substituted zinc porphyrins as well [Zn-II(por)] {por = dianion of 5,10,15,20-meso-tetrakis(aryl)-porphyrin; aryl = phenyl (TPP), p-Bu-t-phenyl (TBPP), m-Cl-phenyl (TOFF)). The respective products [Zn-II(C24H16N2O2Br5)(2)] (3), [Zn-II(C32H32N2O2Br5)(2)] (4), and [Zn-II(C24H14N2O2Cl2Br8)(2)] (5) have been isolated in good to moderate yields and characterized by elemental analysis and UV-vis, H-1 NMR, and mass spectrometry. Additional bromination reaction of 1 with 8 equiv of NBS in a chloroform/methanol mixture led (after the two-sided ring opening) to nonmetalated brominated bi(pyrrole) product, C38H34N2O4Br4 (6). The detailed structures of complexes 1, 2, 3, and 6, available in a single crystal form, have been confirmed by X-ray diffraction analysis.