Conformationally designed, non-planar porphyrins afford new classes of structurally distinct chromophores with significantly altered optical, redox, magnetic, radical and excited state properties. The synthetic, non-planar porphyrins model and illustrate the consequences of the skeletal deformations and plasticity increasingly observed in crystal structures of protein complexes comprising porphyrinic chromophores and prosthetic groups. Conformational variations thus offer attractively simple mechanisms for modulating the physicochemical properties of porphyrins in vivo and in vitro.