Three types of Eu3+-doped LaPO4 three-dimensional (3D) microstructures have been hydrothermally prepared by adjusting pH value and the molar ratio of La3+ and Eu3+ to phosphorus of Na5P3O10 (Ln/P) at 180 degrees C. As the pH value was 0.15 and the molar ratio of Ln/P was in the range of 1/1 to 1/4, 5 mu m urchinlike spheres composed of long nanorods of hexagonal LaPO4:Eu were obtained. As the pH value was 1.00 and the molar ratio of Ln/P was 1/1, 3 mu m hollow spheres consisting of short nanorods of monoclinic LaPO4:Eu were prepared. Keeping the pH value at 1.0 and the molar ratio of Ln/P at 1/4, 6 mu m core-shell spheres of monoclinic LaPO4:Eu formed. Luminescent measurements were performed. Hollow spheres of monoclinic LaPO4:Eu had the strongest emission intensity. However, the emission intensity of monoclinic core/shell structure was even lower than that of hexagonal LaPO4:Eu urchinlike spheres. (C) 2010 Elsevier Ltd. All rights reserved.