Uniform hollow Lu2O3:Ln (Ln = Eu3+, Tb3+) phosphors have been successfully prepared via a urea-assisted homogeneous precipitation method using carbon spheres as templates, followed by a subsequent calcination process. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transformed infrared (FT-IR), thermogravimetric and differential thermal analysis (TG-DTA), photoluminescence (PL) spectra, cathodoluminescence (CL) spectra, kinetic decays, quantum yields (QY), and UV-visible diffuse reflectance spectra were employed 10 characterize the samples. The results show that hollow Lu2O3:Ln spheres can be indexed to cubic Gd2O3 phase with high purity. The as-prepared hollow Lu2O3:Ln phosphors are confirmed to be uniform in shape and size with diameter of about 300 rim and shell thickness of approximate 20 nm. The possible formation mechanism of evolution from the carbon spheres to the amorphous precursor and to the final hollow Lu2O3:Ln microspheres has been proposed. Upon ultraviolet (UV) and low-voltage electron beams excitation, the hollow Lu2O3:Ln (Ln = Eu3+, Tb3+) spheres exhibit bright red (Eu3+, D-5(0)-F-7(2)) and green (Tb3+, D-5(4)-F-7(5)) luminescence, which may find potential applications in the fields of color display and biomedicine.