Lanthanide ions (Ln3+)-doped CaF2 luminescent nanoparticles exhibit unique optical properties and represent promising candidates for bioapplications; however, their inherent weak luminescence intensity greatly limits their application, especially for Nd3+-sensitized ones. We have doped Ln3+ ions along with Na+ ion into CaF2 lattice to maintain charge neutrality and investigated the influence of Na+ ion on the 800 nm triggered upconversion process. As compared with Na+-free (shell layer) nanoparticles, the crystallinity of Na+-ion-codoped ones has been improved greatly, and the average lifetimes of the excited Nd3+, Yb3+, and Er3+ states have been prolonged after Na+ ion codoping in the sensitizing shell. Thus the energy-transfer efficiency from sensitizers (Nd3+) to activators (Er3+) has been increased by 67%. As a result, the upconversion luminescence intensity of the nanoparticles with suitable Na+ doping reaches 67 times higher than Na+-free nanoparticles upon 800 nm irradiation, although fewer Ln3+ io...