In this study, we report on the structural, magnetic, and optical properties of Tb3+-doped CeF3 nanocrystals prepared via a polyol-assisted route, followed by calcination. X-ray diffraction analysis and electron microscopy investigations have shown the formation of a dominant Ce0.75F3 nanocrystalline phase (of about 99%), with a relatively uniform distribution of nanocrystals about 15 nm in size. Magnetization curves showed typical paramagnetic properties related to the presence of Ce3+ and Tb3+ ions. The magnetic susceptibility showed a weak inflexion at about 150 K, assigned to the cerium ions’ crystal field splitting. Under UV light excitation of the Ce3+ ions, we observed Tb3+ green luminescence with a quantum yield of about 20%.