A wet chemical approach was employed for the preparation of LiEu(PO3)(4) nanoparticles. XRD, Raman spectroscopy, TEM, SAED, and IR measurements were used in order to determine the crystal structure and morphology of the obtained product. Complete optical studies including absorption, excitation, emission, and kinetic measurements were performed. At least two components of the D-5(0) -> F-7(0) transition were found, indicating the existence of more than one crystallographic position of the Eu3+ ions. Asymmetry parameter R as well as the covalence of the Eu-O bond were found to decrease with the grain growth.