The investiga tion reported is the study of electronic structure of the intermetallic compound Gd5Ge2Si2 and its Co-substitution i.e. Gd5Ge1.9Si2Co0.1 with the help of X-ray photoelectron spectroscopy (XPS). The investigations reveal the crystallization of the compounds to be in a single phase with Orthorhombic structure. The XPS spectra disclose the signature peaks of the various orbitals of the constituent elements of the compounds. Though a subtle shift in the binding energy values is observed. The deconvoluted XPS spectra provides the interaction of the core of the compounds with different neighbours. Deconvolution shows that for Gd(3d) spectra the strongest bonding is for Gd-Ge bond with a binding energy value of ∼ 1190 eV for both the compounds. Also, for Si(2p) spectra this value is close to 102 eV for Si-Ge bond.