Two meso-tetraphenylporphyrin (H2TPP) derivatives with different central metal ions, namely ZnTPP, CuTPP, were synthesized, and characterized by a series of spectroscopic methods. Their self-assembly behaviors in mixed solvents without surfactant were systematically investigated. The morphology of the thus produced nanoarchitectures could be efficiently controlled. Nanoslices can be manufactured when a volume of cyclohexane is involved, octahedrons can be produced when a mixed solvent of chloroform and isopropanol is employed, while four-leaf clover-shaped structures can be produced with a large volume of methanol injected. The nanostructures have been characterized by electronic absorption, scanning electron microscopy (SEM) and photoelectric conversion techniques. The internal structures of the nanostructures are well described by XRD. The nanostructures exhibit a power conversion under illumination intensity of 2.3 mW cm−2. The present result appears to represent an effort toward controlling the morphology of self-assembled nanostructures of porphyrin derivatives via synthesis through introduction of metal–ligand and solvent interaction. Nevertheless, the fundamental study will be helpful to understand photoinduced energy/charge transport in an organic interface and this might also serve as promising building blocks for nanoscale power sources for potential application in solar energy technologies and organic electronics and optoelectronics.