Monodisperse EuF3 hollow spheres with diameter of about 95 nm were firstly synthesized using Eu(OH)CO3 nanospheres as template. Control experiments indicated the morphology and crystal quality of the final products were greatly influenced by the synthesis parameters such as pH value, temperature and reactant concentration. Subsequently, a possible growth mechanism for the nano-sized hollow sphere was proposed and the photoluminescence (PL) properties of as-prepared EuF3 products were also intensively studied. Furthermore, this method could serve as a general route to prepare other rare earth fluorides hollow spheres. (C) 2011 Elsevier B.V. All rights reserved.