Three novel mixed (phthalocyaninato)(porphyrinato) yttrium double-decker complexes appended with one metal-free porphyrin chromophore at the pant, meta, and ortho position, respectively, of one meso-phenyl group of the porphyrin ligand in the double-decker Unit through ester linkage, 3-5, have been designed, synthesized, and spectroscopically characterized. The photophysical properties of these three isomeric tetrapyrrole triads were comparatively investigated along with the model compounds metal-free tetrakis(4-butyl)porphyrin H-2-TBPP (1) and mixed [1,4,8,11,15,18,22,25-octakis(butyloxyl)phthalocyaninato][tetrakis(4-but yl)porphyrinato] yttrium double-decker complex HY[Pc(alpha-OC4H9)(8)](TBPP) (2) by steady-state and transient spectroscopic methods. The fluorescence of the metal-free porphyrin moiety attached through ester linkage at the meta and ortho position of one meso-phenyl group of porphyrin ligand in the double-decker unit in triads 4 and 5 is effectively quenched by the double-decker unit, which takes place in several hundred femtoseconds. However, the fluorescence of the metal-free porphyrin moiety attached at the par position of one meso-phenyl group of porphyrin ligand in the double-decker unit in triad 3 is only partially quenched, clearly revealing the effect of the position of porphyrin-substituent on the photophysical properties of the triads. Furthermore, the molecular structures of 3-5 were simulated using density functional theory calculations. It was found that the relative orientation between the metal-free porphyrin moiety and the double-decker unit for compound 3 is crossed, while those for compounds 4 and 5 are open- and closed-shellfish-like, respectively, which is suggested to be responsible for their different intramolecular fluorescent quenching efficiency.