The first substituted bis(porphyrin) complexes, Zr-porph)(porph-X) (X = NO2, NH2, where X replaces one of the beta-pyrrole hydrogens), have been prepared. Introduction of an electron-withdrawing or -donating group alters the electronic structure of the molecule, as evidenced by the electronic spectra and cyclic voltammetry. The electronic spectra of the pi-radical cations and dications confirm that the interporphyrin pi-pi interactions are affected by beta substitution. H-1 NMR of Zr(TTP)(TTP-X) shows that the two porphyrin macrocycles do not rotate with respect to each other even at 150-degrees-C.