Spherical like Y2O3nanostructures doped with Er3+and Yb3+ions have been synthesized by a facile hydrothermal method. The samples were prepared by using different precipitant agents in the synthesis process. The phosphors were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and photoluminescence spectroscopy. Effects of the precipitant agents on structural, morphological, and photoluminescence properties of Y2O3:Er3+-Yb3+are studied and discussed. XRD analysis indicates that all samples, prepared with different precipitant agents, present the same cubic phase. Electron microscopy measurements show regular spherical shapes with size diameter depending on precipitant agent. Photoluminescence reveals that the samples have strong green (563 nm) and red (660 nm) emissions corresponding to4S3/2 → 4I15/2and4F9/2 → 4I15/2transitions of Er3+ions, respectively. The nanophosphors prepared with both Thiourea and Lithium Hydroxide exhibit the stronger visible upconversion luminescence under 980 nm diode laser excitation.