A novel phosphor, Gd2MoB2O9:Eu3+ has been synthesized by solid-state reaction and its photoluminescence in UV-VUV range are investigated. A sharp excitation band is observed in the region of 120–135 nm, which is related to the charge-transfer (CT) band of Gd3+. The broad band around 135–160 nm can be assigned to the BO3 host absorption. The broad bands around 248 nm are assigned to the CT band of Eu3+-O2-. The phosphors emit strong red luminescence centered at about 591 nm, 614 nm and 626 nm due to the5D0–7F1 and 5D0–7F2 transitions of Eu3+. The main emission peak under 254 and 147 nm excitations also shows different shifts with increasing Eu3+ concentration. This could be due to the different luminescence sites selected at high doping concentrations of Eu3+. Gd2MoB2O9:Eu3+ shows the pure red emission under both 254 and 147 nm excitations.