A series of mono-, double-, and tri-doped LiNbO3 crystals with vanadium were grown by Czochralski method, and their photorefractive properties were investigated. The response time for 0.1 mol% vanadium, 4.0 mol% zirconium, and 0.03 wt.% iron co-doped lithium niobate crystal at 488 nm was shortened to 0.53 s, which is three orders of magnitude shorter than the mono-iron-doped lithium niobate, with a maintained high diffraction efficiency of 57% and an excellent sensitivity of 9.2 cm/J. The Ultraviolet-visible (UV-Vis) and OH− absorption spectra were studied for all crystals tested. The defect structure is discussed, and a defect energy level diagram is proposed. The results show that vanadium, zirconium, and iron co-doped lithium niobate crystals with fast response and a moderately large diffraction efficiency can become another good candidate material for 3D-holographic storage and dynamic holography applications.