Lutetium oxyorthosilicate Lu2SiO5(LSO) and pyrosilicate Lu2Si2O7(LPS) activated by Ce3+or Pr3+are known to be effective and fast scintillation materials for the detection of X-rays and γ-rays. Their performances can be further improved by co-doping with aliovalent ions. Herein, we investigate the Ce3+(Pr3+)→Ce4+(Pr4+) conversion and the formation of lattice defects stimulated by co-doping with Ca2+and Al3+in LSO and LPS powders prepared by the solid-state reaction process. The materials were studied by electron paramagnetic resonance (EPR), radioluminescence spectroscopy, and thermally stimulated luminescence (TSL), and scintillation decays were measured. EPR measurements of both LSO:Ce and LPS:Ce showed effective Ce3+→Ce4+conversions stimulated by Ca2+co-doping, while the effect of Al3+co-doping was less effective. In Pr-doped LSO and LPS, a similar Pr3+→Pr4+conversion was not detected by EPR, suggesting that the charge compensation of Al3+and Ca2+ions is realized via other impurities and/or lattice defects. X-ray irradiation of LPS creates hole centers attributed to a hole trapped in an oxygen ion in the neighborhood of Al3+and Ca2+. These hole centers contribute to an intense TSL glow peak at 450–470 K. In contrast to LPS, only weak TSL peaks are detected in LSO and no hole centers are visible via EPR. The scintillation decay curves of both LSO and LPS show a bi-exponential decay with fast and slow component decay times of 10–13 ns and 30–36 ns, respectively. The decay time of the fast component shows a small (6–8%) decrease due to co-doping.