In this study, computational and experimental methods are employed to study the optical properties of YVO 4 induced by europium dopant. Atomistic modeling is used to predict the symmetry and the detailed geometry of the dopant site. This information is then used to calculate the crystal-field parameters. Eu-doped YVO 4 nanopowders are prepared via a sol–gel proteic technique. Thereafter, multiple techniques including X-ray diffraction (XRD) and transmission electron microscopy (TEM) are used to examine the structural properties and surface morphology of the YVO 4 :Eu 3+ phosphors. The optical properties are studied using photoluminescence (PL) and radioluminescence (RL) spectroscopy performed at room temperature. The transition energy of the Eu 3+ -doped material is compared with the theoretical results. The intensity parameters Ω 2 and Ω 4 of Eu 3+ in the YVO 4 matrix are calculated with the Judd-Ofelt approach.