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We report on a red-emitting ScVO₄:Bi³⁺ phosphor which does not show excitation at energies below 2.88 eV (430 nm). X-ray diffraction, time-resolved, and quantitative photoluminescence (PL) spectroscopy were employed to characterize relations between crystal structure and luminescence properties of the material. Results show that incorporation of Bi³⁺ renders the blue photoemission of blank ScVO₄ to red. Dynamic luminescence analysis between 10 and 300 K reveals a complicated dependence of energy transfer from VO₄^3– groups to Bi³⁺ ions and population redistribution of ³P₁ and ³P₀ of Bi³⁺ on temperature. This reflects in distinct changes in the luminescence decay functions. That is, a dramatic decrease of Bi³⁺ luminescence lifetime occurs from hundreds to only several microseconds. Density functional theory is employed to reveal how the unusual red Bi³⁺ luminescence comes, and results …