Gadolinium silicate, (Gd2SiO5) co-doped with Ce and Eu has been found to exhibit enhanced luminescence efficiency, which makes it a promising material for use in scintillators and phosphors. It has excellent scintillation properties such as high density and high Zeff. In this study, we used density functional theory (DFT) calculations within the Wien2k software to investigate the effect of Ce and Eu concentration and native defects on the electronic structure and optical properties of Ce and Eu co-doped Gd2SiO5. We utilized the DFT + U method to treat the localized 4f electrons of Ce and Eu. Our results indicate that the electronic structure and optical properties of Ce and Eu co-doped Gd2SiO5 are significantly affected by the concentration of the dopants and presence of native defects. We found that increasing the concentration of Ce and Eu dopants leads to a shift in the bandgap to lower energies, resulting in enhanced absorption and emission spectra. Moreover, our calculations reveal that presence of oxygen vacancies and Gd interstitials can induce new defect levels in the bandgap, which may affect the luminescence properties of the material. Our study provides valuable insights into the atomic-level mechanisms that govern the luminescence properties of Ce and Eu co-doped Gd2SiO5 which can aid in the design and optimization of luminescent materials for various applications.