Eu3+-doped Y2O3-based luminescent materials can be used as a scintillator for electron or high energy β-ray irradiation, which are essential for applications such as electron microscopy and nuclear batteries. Therefore, it is essential to understand their defect mechanisms and to develop materials with excellent properties. In this paper, Y2O3-based transparent ceramics with different Eu3+ doping concentrations were prepared by solid-state reactive vacuum sintering. This series of transparent ceramic samples exhibits strong red emission under electron beam excitation at the keV level. However, color change appears after the high-energy electron irradiation due to the capture of electrons by the traps in the Y2O3 lattice. Optical transmittance, laser-excited luminescence, X-ray photoelectron spectroscopy (XPS), and other analyses indicated that the traps, or the color change, mainly originate from the residual oxygen vacancies, which can be suppressed by high Eu doping. Seen from the cathodoluminescence (CL) spectra, higher doping concentrations of Eu3+ showed stronger resistance to electron irradiation damage, but also resulted in lower emissions due to concentration quenching. Therefore, 10% doping of Eu was selected in this work to keep the high emission intensity and strong radiation resistance both. This work helps to enhance the understanding of defect formation mechanisms in the Y2O3 matrix and will be of benefit for the modification of scintillation properties for functional materials systems.