A pentaporphyrinic assembly was formed in one step, quantitatively, from a gable like zinc(II) bis-porphyrin and a free-base meso-tetrakis(4-pyridyl)porphyrin, because of the formation of four zinc-nitrogen coordination bonds. The X-ray crystal structure obtained shows a symmetrical structure, the free-base porphyrin being located at the center of a square formed by the four zinc atoms of the two zinc(II) bis-porphyrins. The two phenanthrolines connecting the zinc porphyrins are respectively above and below the plane of the central free-base porphyrin because of favorable CH-pi interactions between several porphyrinic assemblies within the crystal. Spectrophotometric and spectrofluorimetric titrations and studies reveal a high association constant for the porphyrinic assembly in the order of 10(14) M-2. As expected, energy transfer from the zinc porphyrin component to the central free-base porphyrin quenches the fluorescence of the zinc porphyrin components whereas no sensitization of the emission of the free-base porphyrin was observed. Hypotheses on this unusual behavior are discussed.