La3PO7:Eu3+ samples were prepared by combustion and annealing and characterized by X-ray diffraction and transmission electron microscopy. It was found that the average size of the particles is about 80 nm. The red emission from the 5D0 → 7F2 transition of the Eu3+ ions under ultraviolet light excitation is much stronger than the orange emission from the 5D0 → 7F1 transition. The emission spectra, charge transfer band, laser selective excitation spectra, and time-resolved spectra indicate that symmetry of the local environment of Eu3+ lacks an inversion center and Eu3+ ions occupy at least two types of sites in the La3PO7 crystal. The superior color chromaticity compared to other phosphates and borates doped with Eu3+ means La3PO7:Eu3+ may have potential as a luminescent material.