By altering the temperature and solvents, we have synthesized hydrated and dehydrated Eu3+/Tb3+-doped REPO4 (RE=Y, La, and Gd) nanophosphors via a solvo-thermal technology. X-ray powder diffraction and scanning electronic microscopy reveal that they have different structures and different morphologies. REPO4 prepared under subsequent heating at 80 degrees, 120 degrees, and 160 degrees C for 1 day, respectively, present larger particle size than that formed by heating at 160 degrees C for 3 days. Moreover, at the same temperature of 160 degrees C and pH 3, three different solvents (ethanol, N,N-dimethylformamide (DMF), and water) were used, whose influence on the microstructure of LaPO4 has been examined. As a result, LaPO4 samples from anhydrous ethanol solvent show a pure hexagonal phase and nanowire morphology, just like that prepared from the water solvent. On the other hand, the microstructure of LaPO4 samples from DMF-H2O-mixed solvents have been changed: with the increasing volume ratio of DMF to H2O, the crystal phase of LaPO4 has been changed from hexagonal phase to monoclinic phase and the morphology from nanowires to nanoparticles. Finally, the photoluminescence properties of these Eu3+ (Tb3+)-activated rare earth phosphates have been investigated, indicating that the photoluminescent behavior are related to their crystal phases and microstructures.