A series of 1,3,5-phenylene-based rigid dendritic porphyrins were synthesized by Suzuki coupling between a porphyrin core and dendron units. The intramolecular energy transfer was studied by absorption and fluorescence spectroscopies. The encapsulation of the porphyrin core within the 1,3,5-phenylene dendron units was found to provide highly efficient energy transfer from the dendron units to the porphyrin core. The dendritic wedge structure affected the energy transfer efficiency. The 1,3,5-phenylene-based rigid dendron units act as highly efficient light-harvesting antennae. These dendritic porphyrins have also been examined as C-60 hosts and substrate-selective oxidation catalysts. The attachment of the second generation of 1,3,5-phenylene-based dendron units with the porphyrin core enabled a stable inclusion of C60 in toluene. Furthermore, the size and shape of the nanospace in the rigid dendritic porphyrins were found to affect the selectivity of substrates in the catalytic olefin oxidations.