The concept of "slow release anions for the assembly of crystals" was successfully carried out through a facile, effective and environmental friendly supersonic and microwave co-assistance (SMC) approach at very low temperature in less than 40 mm. It has been found that the rational design of multiple irradiations, lanthanide contraction and fluoride sources would make it possible to control both the crystalline phases (hexagonal or orthorhombic) and the microstructures (including nanoparticles, nanoplates or micro-meter scale particles). The photo-luminescent properties of EuF3 and TbF3 revealed that characteristic red and green emissions can be excited by multiple wavelengths. Moreover, the results demonstrated that there are efficient energy transfers from Gd3+ to Eu3+ and Tb3+ in GdF3: Eu3+ and GdF3: Tb3+ phosphors based on this new method. (C) 2014 Elsevier B.V. All rights reserved.