In this work, a metal-mediated assembling strategy has been used to organize a series of new assemblies based on tetrapyridylporphyrin () on nanostructured TiO2 electrode surfaces, wherein the metal ions (, = Zn(2+), Cd(2+), Hg(2+) and Mn(2+)) bridge the pyridyl units of and (E)-4-[(pyridin-4-ylmethylene)-amino]benzoic acid (), resulting in a assembled mode. The assembled structures were characterized by transmission electron microscopy (TEM), computational calculations, energy-dispersive X-ray spectroscopy (EDX), IR, UV-vis absorption and fluorescence spectra. The performances of the assembly-sensitized solar cells were also measured under an irradiance of 100 mW cm(-2) AM 1.5G sunlight. Photoelectrochemical results reveal a relatively large photocurrent of the device. Simultaneously, a large open-circuit photovoltage and a significantly improved conversion efficiency of the device are also observed. These findings may serve as another good testing ground for the fabrication of supramolecular solar cells in future.