Using static and time-resolved measurements, dynamics of non-radiative relaxation processes have been studied in self-assembled porphyrin triads of various geometry, containing the main biomimetic components, Zn-porphyrin dimers, free-base extra-ligands (porphyrin, chlorin or tetrahydroporphyrin), and electron acceptors A (quinone or pyromellitimide). The strong quenching of the dimer fluorescence is due to energy and sequential electron transfer (ET) processes to the extra-ligand (~0.9-1.7 ps), which are faster than a slower ET (34-135 ps) from the dimer to covalently linked A in toluene at 293 K. The extra-ligand S 1 -state decay (τ S =940-2670 ps) is governed by competing processes: a bridge (dimer) mediated long-range (r D A =18-24 Å) superexchange ET to an acceptor, and photoinduced hole transfer from the excited extra-ligand to the dimer followed by possible superexchange ET steps to low-lying charge transfer states of the triads. The subsequent ET steps dimer->monomer->A taking place in the triads, mimic the sequence of primary ET reactions in photosynthetic reaction centers in vivo.