YVO4: 10%RE3+ (RE = Eu, Sm, Dy, Er) nanophosphors have been synthesized by a facile modified hydrothermal technology to obtain the high purity. The key procedure for this hydrothermal process is the adding order of precursors, in which excess sodium vanadate should be added in the solution of rare earth nitrates. The microstructure (crystal phase, morphology, particle size) of these phosphors are characterized by x-ray powder diffraction, scanning electron microscope, and transmission electron microscope, which indicates that there are some cube-like crystals with tetragonal zircon structure and the average particle size is approximately 40 nm. The luminescent behaviors for the four rare earth ion-activated YVO4 nanophosphors have been studied, and, for YVO4: 10%Eu3+ nanophosphors in particular, it is found that a different hydrothermal process influences the phase composition, microstructure, and photoluminescence. This result suggests that the hydrothermal synthesis process (by adding sodium vanadate to the solution of rare earth nitrates) is favorable for YVO4 nanophosphor to obtain pure phase, small particle size, long luminescent lifetime, and high luminescence quantum efficiency.