The NaCaPO 4 :Eu 3+ phosphor was synthesized by the sol-gel method. The structure and luminescence properties of the phosphor were analyzed by thermogravimetricdifferential thermal analysis (TG-DTA), Fourier-transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), transmission electron microscopy (TEM) and fluorescence spectroscopy. TG-DTA results show that NaCaPO 4 phase can be formed after 700 C. FTIR spectra confirmed the existence of PO 4 units. XRD results show that the sample is a pure NaCaPO 4 orthorhombic crystal phase. The TEM diagram shows that the sample has good uniformity. The NaCaPO 4 :Eu 3+ emits orange light under 394 nm excitation. The optimal doping concentration is 3 mol%. The reason for concentration quenching is caused by multipolar interaction. Through further analysis of the charge transfer band and the spectrum at 5 D 0 ! 7 F 0 transition of the NaCaPO 4 : Eu 3+ phosphor, the reason for the orange light of the phosphor is owing to the different Eu 3+ occupancy which is explained in detail.