The photophysical properties of porphyrin-based assembled molecular system was investigated using steady-state fluorescence and transient absorption. The obtained results indicate the existence of energy transfer process from the triplet state of donor ZnP to the acceptor Fe(Cl)P, mediated by the bridge molecule. At room temperature, the fluorescence of ZnP was quenched dramatically with the presence of acceptor Fe(Cl)P, implying the energy transfer between donor and acceptor. By comparison of the triplet state lifetime of ZnP in reference and assembled system, it was observed the excitation energy of donor's triplet state is quenched by a factor of 5, and the rate constant for energy transfer is around 7.2×105 s-1. The temperature dependence of energy transfer rate constant indicates the influence of conformation on the electronic coupling between donor and acceptor mediating by the bridge molecule. Considering the spatial distance between donor and accepter being upto 2.5 nm, it could be concluded that superexchange mechanism via bridge dominates the deactivation of excited triplet state of ZnP in the assembled porphyrin dimer.