Orange-emitting Eu2+ activated Ba4Li2B10O20 phosphors were synthesized by a traditional solid-state reaction at elevated temperature. The synthesis and luminescent properties of the phosphors were studied in detail. The Ba4Li2B10O20: Eu2+ has shown a broad and intense orange emission band centered at 585 nm corresponding to 330 nm excitation wavelength. The critical quenching concentration of Eu2+ in Ba4Li2B10O20 was about 0.04, and the corresponding concentration quenching mechanism was verified to be the electric multipolar interaction. The fluorescence lifetime of Eu2+ emission and the thermal-dependent luminescence property have been investigated. The results suggest that Ba4Li2B10O20: Eu2+ phosphors have potential applications in UV-excited LEDs.