Cubic phase NH 4 Eu 3 F 10 nanospheres with controllable sizes were synthesized via a modified hydrothermal route by varying the dosage of ammonium hydroxide solution. Dependence of structure and morphology on the dosage of ammonia water and reaction time were investigated by X-ray powder diffraction (XRD) and transmission electron microscopy (TEM). Being unstable, NH 4 Eu 3 F 10 decomposed into EuF 3 and NH 4 F during the long-time hydrothermal treatment. EDTA, as the chelation agent of Eu 3+ and the capping ligand on the surface of as-obtained nanospheres, showed different chelating abilities depending on the dosage of ammonium hydroxide solution. Increasing the amount of ammonia not only decreased the effective concentration of Eu 3+ , but also decelerated the growth of NH 4 Eu 3 F 10 nanospheres and stabilized them by reducing the surface energy. Given the satisfactory hydrophilicity, biocompatibility, and luminescence, the as-obtained nanospheres were applied as promising agents for cell imaging by presenting high contrast.