Ground state and time resolved excited state optical absorption spectra and luminescence spectra are reported for La-2(OEP)(3), Eu-2(OEP)(3), and Ce-2(OEP)(3) (OEP = 2,3,7,8,12,13,17,18-octaethylporphyrinate). The porphyrin macrocycles in these molecules are strongly coupled due to their mean separation of less than or equal to 3.5 Angstrom. The triple deckers show many optical properties analogous to those found for double decker porphyrin sandwich complexes, including features not exhibited by porphyrin monomers. Following excitation, the lowest (1)(pi,pi*) state of La-2(OEP)(3) decays in similar to 10 ps predominantly to the phosphorescent (3)(pi,pi*) state, which lives for similar to 10 mu s. The lowest (1)(pi,pi*) state of Eu-2(OEP)(3) also decays rapidly and with high yield to the lowest (3)(pi,pi*) state, which has a rather short lifetime of 630 ps. The lack of luminescence from Eu-2(OEP)(3) is ascribed to deactivation of the (3)(pi,pi*) State through one or more low-energy ligand-field states of the metal ion. Ce-2(OEP)(3) is also nonluminescent. Unlike La-2(OEP)(3) and Eu-2(OEP)(3), the (1)(pi,pi*) lifetime of 7 ps for Ce-2(OEP)(3) largely reflects deactivation within the singlet manifold. The decay of (1)(pi,pi*) to the ground state likely involves low-lying (f,f) states, although a charge transfer state may play a role. The small (similar to 20%) population of (3)(pi,pi*) that forms from (1)(pi,pi*) also decays rapidly (tau similar to 300 ps), again via ligand-field states of the metal ions. These combined results further demonstrate the importance of (i) pi,pi interactions in defining the electronic properties of chromophores brought within van der Waals distance and (ii) metal-centered excited states in determining the relaxation rates and pathways following photoexcitation of tetrapyrrole complexes.