YVO₄: Bi³⁺, Eu³⁺nanophosphors are prepared by the citrate-assisted low-temperature wet chemical synthesis. When the colloidal solution is aged at 60°C, the crystalline YVO₄: Bi³⁺, Eu³⁺ nanorods are formed from the amorphous gel precursors, as confirmed by transmission electron microscopy and X-ray diffractometry (XRD). YVO₄: Bi³⁺, Eu³⁺ nanophosphors emit red through energy transfer from Bi³⁺ to Eu³⁺ under near-UV-light excitation. The emission intensity increases with increasing the fraction of the crystalline phase during aging. The excitation peak corresponding to Bi³⁺–V⁵⁺ charge transfer relative to those of O²⁻–V⁵⁺ and O²⁻–Eu³⁺ charge transfers gradually becomes strong until the completion of the crystallization, although the contents of individual Bi³⁺ and Eu³⁺ ions incorporated into YVO₄ keep constant. When the aging is continued after the completion of the crystallization, the content of incorporated Bi³⁺ gradually increases, and hence the emission intensity decreases as a result of the energy migration among Bi³⁺ ions. These results suggest that in addition to the fraction of the crystalline phase and the contents of incorporated Bi³⁺ and Eu³⁺ ions, the local chemical states around Bi³⁺ play significant roles in photoluminescence properties.