Nanostructured tetragonal LaVO4 with sheaf-like and prickly spherical morphologies has been hydrothermally synthesized with the assistance of ethylenediaminetetraacetic acid (EDTA). In the hydrothermal process, EDTA not only acts as a chelating reagent to facilitate the formation of t-LaVO4, but also acts as a surface capping agent to adhere to the newly created surface and to promote the crystal splitting. t-LaVO4 nanostructures with different morphologies can be achieved by adjusting the molar ratio of EDTA/La3+, the concentration of La3+, and the total volume of the reaction mixture, which result in the change of the crystal growth rate. Nanostructured Eu3+-doped t-LaVO4 was also synthesized and showed intense red emission under near UV-light excitation.