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The Gd2O2CO3:Eu3+ with type-II structure phosphor was successfully synthesized via flux method at 400℃ and their photoluminescence properties in vacuum ultraviolet (VUV) region were examined. The broad and strong excitation bands in the range of 153-205 nm owing to the CO32- host absorption and charge transfer (CT) of Gd3+-O2- were observed for Gd2O2CO3:Eu3+. Under 172 nm excitation, Gd2O2CO3:Eu3+ exhibited strong red emission with good color purity, indicating Eu3+ ions located at low symmetry sites and the chromaticity coordination of luminescence for Gd2O2CO3:Eu3+ was (x=0.652, y=0.345). The photoluminescence quenching concentration of Eu3+ excited by 172 nm for Gd2O2CO3:Eu3+ was about 5%. Gd2O2CO3:Eu3+ would be a potential VUV-excited red phosphor applied in mercury-free fluorescent lamps.