Atomistic simulation is performed to study the defect properties and spectroscopy in the MgGa2O4 structure. The calculations indicate that the most favorable type of intrinsic defect is generated by the cation antisite defect, in which there is an exchange of positions between Mg2+ and Ga3+ ions. The calculation also indicates that the incorporation of Eu3+ dopant at the Ga3+(2) site is the most energetically favorable. According to a spectroscopic study using the crystal field approach, Eu3+ replaces the Ga3+ site occupying a combination of C4 and C4h symmetries while maintaining the same amount of the non‐null crystal field parameters. This result is important for the reproduction of experimental energy sublevels and ΔE (7F1) manifold splitting.