Reaction between Eu(NO3)3 and NH4F in aqueous media was applied to produce EuF3 doughnut-like aggregates with a diameter of 200–500 nm and thickness of 50–150 nm composed of nanoparticles with a mean diameter of 16 nm. The impregnation, sorption and mechanochemical treatment were used for surface modification of EuF3 doughnut-like particles with 1,10-phenanthroline and sodium dibenzoylmethanate which are sensitizing ligands for Eu3+ luminescence. The data of transmission electron microscopy, elemental analysis, Fourier transform infrared spectroscopy, and luminescence spectroscopy have proved that the organic ligands are coordinated to surface Eu3+ ions, forming surface complexes. The surface modification of the EuF3 nanoparticles with sodium dibenzoylmethanate and 1,10-phenanthroline leads to increase in the luminescence intensity at 612 nm (5D0→7F2 transition) in comparison with the luminescence intensity of the unmodified EuF3 nanoparticles. Energy transfer from the ligand to Eu3+ ion in the surface complexes makes a main contribution to this effect.