The new red-emitting phosphors of Eu3+-doped borotungstate Gd4B2WO12 were prepared by the high-temperature solid-state reaction. The phosphors were characterized by X-ray powder diffraction technique. The photoluminescence excitation and emission spectra, the fluorescence decay curves and the dependence of luminescence intensity on temperature were investigated. The phosphor can be efficiently excited by near UV light to realize an intense red luminescence (618 nm) corresponding to the electric dipole transition 5D0[RIGHTWARDS ARROW]7F2 of Eu3+ ions. The crystallographic site-occupations of the Eu3+ ions in Eu4B2WO12 were investigated by the site-selective excitation and emission spectra, and the fluorescence decay curves in the 5D0[RIGHTWARDS ARROW]7F0 region using a pulsed, tunable, and narrowband dye laser. The concentration quenching of the red luminescence together with the thermal stability were discussed on the base of the Eu3+ site-distributions in Eu4B2WO12 host.