V-doped MgAl6O10 is grown by the conventional Czochralski method. The crystal structure and the cell parameters are analyzed through X-ray diffraction experiments. The absorption and emission spectra are investigated. Under pumping at 324 nm, the emission spectra of V-doped MgAl6O10 obtain two emission peaks at the wavelengths of 471 and 570 nm. Two emission bands of the spectra combine to produce a spectrum that is perceived as white by the naked eye. Therefore, V-doped MgAl6O10 single crystal can be applied as substrate for phosphor-free ultraviolet (UV)-white light-emitting diodes (LEDs).