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The fabrication and luminescent performance of novel phosphors Na₂YMg₂V₃O₁₂:Dy³⁺ were investigated by a conventional solid-state reaction method. Under near-UV light, the Na₂YMg₂V₃O₁₂ host self-activated and released a broad emission band (400−700 nm, with a peak at 524 nm) ascribable to charge transfer in the (VO₄)^3− groups. Meanwhile, the Na₂YMg₂V₃O₁₂:Dy³⁺ phosphors emitted bright yellow light within both the broad emission band of the (VO₄)^3- groups and the sharp peaks of the Dy³⁺ ions at 490, 582, and 663 nm at a quenching concentration of 0.03 mol. The emission of the as-prepared Na₂YMg₂V₃O₁₂:Dy³⁺ phosphors remained stable at high temperatures. The obtained phosphors, commercial Y₂O₃:Eu³⁺ red phosphors, and BaMgAl₁₀O₁₇:Eu²⁺ blue phosphors were packed into a white light-emitting diode (WLED) device with a near-UV chip. The designed WLED emitted bright white light with good chromaticity coordinates (0.331, 0.361), satisfactory color rendering index (80.2), and proper correlation to a color temperature (7364 K). These results indicate the potential utility of Na₂YMg₂V₃O₁₂:Dy³⁺ phosphor as a yellow-emitting phosphor in solid-state illumination.