Layered magnetic heterostructures are very promising candidates in spintronics in which the influences of interfaces, surfaces and defects play a crucial role. X-ray photoelectron spectroscopy (XPS) study has been performed for studying in detail the chemical state and electronic structure of Co2FeAl (CFA) Heusler alloy interfaced with Si substrates. XPS survey scan spectra have clearly shown the presence of Fe, Co and Al signal along with the signal due to Si. The presence of Co, Fe and Al signal confirms the formation of CFA alloy phase. Our XPS results support our previous study  on CFA/Si structure in determining the magnetic and transport properties across the interface.