Many recent studies have highlighted the possibility to tailor the physical and chemical properties of porphyrin at the molecular level to design novel catalysts, sensors and devices with applications in electronics, opto-electronics, and so forth. In the present work, we study the electronic properties of 2H-Tetraphenylporphyrin (2H-TPP) on iron (Fe) and iron silicide (Fe 3 Si) onto Si (100) substrate using X-ray and Ultraviolet photoelectron spectroscopy (XPS & UPS). The results revealed that the iron atom is coordinated by TPP molecules on Fe/Si as well as on Fe 3 Si/Si. XPS results provide evidence of the iron coordination with TPP molecules. The UPS analysis evidenced the fine structure in the electronic spectra related to HOMO states below the Fermi level.