LaF3:Eu3+, LaF3:Eu3+@LaF3, LaF3:Eu3+@CeF3 and LaF3:Eu3+@SiO2 nanoparticles were successfully synthesized via hydrothermal route and modified Stöber method. The surface property of LaF3:Eu3+ particle was successfully modified by coating LaF3 and SiO2 shell onto the particle, which resulted in the change of the surface property and luminescence emission of LaF3:Eu3+. It was found that the surface quenchers were decreased and thus the nonradiative pathways were reduced with core/shell structure, which not only enhanced the yellow emission of the sample, but also changed the intensity ratio of the yellow to orange emission. The dependence of the shell property and shell thickness on the luminescence emission spectra were investigated systematically. The current investigation can provide useful information for developing applications in biological imaging, detection, and sensing and other aspects.