Ce3+ and Tb3+-co-doped LaPO4 (LaPO4:Ce/Tb) nanofibers were formed using a simple electro-spinning technique followed by a calcination process. X-ray diffraction (XRD), scanning electron microscopy (SEM), photoluminescence (PL), and kinetic decays were used to characterize the resulting samples. The energy transfer process from Ce3+ to Tb3+ in LaPO4:Ce3+/Tb3+ nanofibers was also studied. The luminescent intensity can be increased through exciting Ce3+ ions in Ce3+/Tb3+-coactivated LaPO4 nanofibers. The emissions intensity of LaPO4:Ce/Tb nanofibers increases gradually with increasing Tb3+ dopant concentration. Whereas, the fluorescence lifetimes for the D-5(4)-F-7(5) transition of the Tb3+ in LaPO4:Ce3+/Tb3+ nanofibers gradually decreased with increasing Tb3+ dopant concentration.