Nd-doped LaVO4 crystals with the concentration up to 0.94 at.% were successfully grown by the Czochralski method. X-ray powder diffraction measurement reveals that this crystal belongs to a monoclinic space group P21/n. Refractive indices of Nd:LaVO4 have been measured with two right angle prisms for the first time to our knowledge and show that they are anisotropic. Its absorption and fluorescence spectra are also investigated. With the Judd–Ofelt theory, the optical parameters calculated are Ω2 = 2.142 × 10−20 cm2, Ω4 = 3.704 × 10−20 cm2, and Ω6 = 2.948 × 10−20 cm2. By these parameters, the absorption oscillator strengths, line strengths, transition probabilities, fluorescence branch ratios, radiative lifetime, and integrated emission cross section are also derived and compared with familiar vanadates, which show that Nd:LaVO4 is a atypical material and has potential applications in the lasers, especially in the pulsed lasers.