Gd2O3:Eu, Li phosphor was synthesized by a modified combinatorial chemistry method, which was based on the polymeric complex using citric acid and ethylene glycol. Different particle growth tendencies were observed both above and below 900degreesC. The luminescent properties of Gd2O3:Eu, Li phosphor were investigated by photoluminescence. The rising phenomena in the initial part of the C-2 site decay curves are elucidated from the rate equation of the excited populations of the C-2 and S-6 site, respectively. To clarify more precisely the distinction of the site symmetry between C-2 and S-6 sites, the decay behavior is analyzed using the direct quenching scheme.