Eu3+ ion-doped BaY2ZnO5 phosphors were synthesized using a vibrating milled solid-state reaction. The phosphors exhibit a series of Eu3+ ion intra-4f excited state 5DJ (J = 3, 2, 1, 0) transitions under an excitation of 395 nm. The maximum photoluminescence intensity for 5D0 → 7F2 transition (625 nm) was obtained at a Eu3+ ion concentration of 40 mol%; quenching occurred at higher concentrations. The critical distance (Rc) for the 5DJ (J = 3, 2, 1) → 7F1 transition was 18.1 Å, which is longer than that of 6.67 Å for the 5D0 → 7F2 transition, indicating that 5DJ (J = 3, 2, 1) is easier for concentration quench because of the cross-relaxation mechanism. The red emission of the BaY1.6Eu0.4ZnO5 phosphor has CIE chromaticity coordinates of (0.66, 0.34), which are close to the NTSC system standard red chromaticity (0.67, 0.33). BaY1.6Eu0.4ZnO5 may thus be potentially applicable as a red phosphor for ultraviolet light-emitting diodes converted in solid-state lighting technology.