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BaY<SUB>2</SUB>ZnO<SUB>5</SUB>:Eu<SUP>3+</SUP> powders were synthesized by a high-energy ball mill (HEB) and a conventional solid-state reaction (SSR) and characterized. The effects of the crystal size on the crystallinity, morphology, structure and luminescence spectra were investigated by X-ray diffraction, field emission-scanning electron microscopy and photoluminescence spectroscopy (PL). The characteristics peak Eu<SUP>3+</SUP> ion intra-4<I>f</I> transitions from the excited states to lower levels are as follows: <SUP>5</SUP>D<SUB>2</SUB>�넂<SUP>7</SUP>F<SUB>J</SUB> (J = 0, 1, 2, 3) transition, <SUP>5</SUP>D<SUB>1</SUB>�넂<SUP>7</SUP>F<SUB>J</SUB> (J = 1, 2, 3) transition, and <SUP>5</SUP>D<SUB>0</SUB>�넂<SUP>7</SUP>F<SUB>J</SUB> (J = 0, 1, 2, 3, 4) transition. The PL intensity of the BaY<SUB>2</SUB>ZnO<SUB>5</SUB>:Eu<SUP>3+</SUP> increased with increasing sintering temperature. Compared to the solid state reaction method, synthesis by high-energy ball milling is simple, easy to carry out, and the raw materials are commercially available.