LaPO 4 :Eu 3 + microspheres were synthesized, using LaCl 3 , EuCl 3 and (NH 4 ) 2 HPO 4 as starting materials. The morphology, formation mechanism, and luminescent property of samples were systemically studied. X-ray diffraction (XRD) and infrared spectroscopy (IR) show that LaPO 4 :Eu 3 + microspheres have a pure monoclinic phase. Cetyltrimethyl ammonium bromide (CTAB) usually forms spherical micelles above a critical micelle concentration, which plays an important role in the formation of LaPO 4 :Eu 3 + microspheres. The excitation spectrum of LaPO 4 :Eu 3 + microspheres consists of several sharp lines due to the direct excitation of the Eu 3 + cations from the ground state to higher levels of the 4f-manifold. The emission intensity of microspheres is higher than irregular particles because of the lowlier surface area. The lifetimes of Eu 3 + ions in the LaPO 4 :Eu 3 + microspheres are determined to be 2.41ms.