LiNbO3 single crystals were implanted at room temperature with Eu+ ions at 70 keV with fluence ranging from 0.5 to 5 × 1016 ions · cm−2. The damage in the implanted layer has been investigated by Channeling Rutherford Backscattering (RBS-C), and the oxidation states of the cations have been determined by x-ray photoelectron spectroscopy (XPS). Following implantation, a fully amorphized layer of 60 nm is generated, even for the lowest fluence employed. Subsequent annealing in air, in the range 800–1250 K, was applied to restore tentatively the crystallinity and promote the substitutional incorporation of Eu in the crystal. Only a partial recrystallization of the damaged layer was observed. For as-implanted samples, XPS spectra clearly reveal europium in Eu2+ and Eu3+ states, and the Nb5+ ions are driven to lower charge states.