YVO4 and YVO4:Ce3+ single crystals doped with 2.0at% CeO2 (or Ce2(CO3)3) were grown by using the Czochralski method. XRD pattern shows that Ce3+ ion enters the YVO4 lattice by occupying the Y3+ sites and the YVO4 crystal structure change little by the addition of Ce ions. The X-ray photoelectron spectroscopy (XPS) shows that the Ce (3d) peak splits into five peaks located at 882.0, 885.8, 902.9, 908.0 and 915.9 eV, which indicates that the Ce3+ and Ce4+ ions coexist in both kind of samples. The excitation spectra of YVO4 and YVO4:Ce3+ crystals are both in the range from 260 nm to 360 nm, due to the charge transfer transition of the O2--V5+ ion pairs of VO43- polyhedron. YVO4 and YVO4:Ce3+ single crystals radiate a wideband blue light centered at 440 nm when excited by 325 nm ultraviolet light, the former corresponds to 3T2→1A1 and 3T1→1A1 transition of VO43-, while the latter corresponds to 5d→4f transition of Ce3+. In YVO4: Ce3+ crystal, the wave functions of Ce3+ overlaps effectively to the π orbital of VO43-, via this interaction the energy can be transfer effectively from VO43- to Ce3+, so that the blue-emitting intensity of Ce3+ is improved significantly. Experimental results show that YVO4: Ce3+ crystal is a potential blue-emitting material for white-emitting LED under ultraviolet excitation.