Red-emitting phosphor BaGd2−xEux(MoO4)4 has been successfully synthesized by a simple sol–gel method. The process of phosphor formation is characterized by thermogravimetric-differential thermal analysis and X-ray diffraction. Field-emission scanning electronic microscopy is used to characterize the size and the shape of the phosphor particles. Photo-luminescent property of the phosphor is also performed at the room temperature. The effects of firing temperature and Eu3+ activator concentration on the photoluminescence (PL) properties are elaborated in detail. PL characterization reveals that the sample with the firing temperature at 800°C and the concentration of Eu3+ at 0.7 shows the most intense emission, and its intensity is about three times stronger than that of phosphor prepared by solid-state method with the same composition and firing temperature. The new red-emitting phosphor shows an intense absorption at 396 nm, which matches well with commercial near-UV light-emitting diode (LED) chips, therefore, it is a good candidate of red phosphor used for near-UV white LEDs.