Three nonequivalent centers of C-s (A, B, and C) in monoclinic phase and C-2 and S-6 centers in cubic phase were identified in the Gd2O3:Eu3+ nanocrystals with spectral techniques. Size dependence in the spectra indicated that the excitations from both host and charge-transfer band (CTB) for the D-5(0) -> F-7(2) transition of Eu3+ ions were nearly equal for a larger size of 135 nm of the cubic phase; however, with decreasing the size to or less than 23 nm, the excitations by the CTB dominated. The variation of excitation leading to the symmetry and energy change in the C-2 and S-6 sites was also observed for larger particle sizes. The Judd-Ofelt intensity parameters Omega(lambda) (lambda = 2, 4) for Gd2O3:Eu3+ nanoparticles were experimentally determined. The parameters Omega(lambda) were found to significantly change with the sizes of Gd2O3:Eu3+ from nanoparticles to bulk material. With decreasing the size from 135 to 15 nm, the quantum efficiencies for D-5(0) reduced from 23.6% to 4.6% due to the increasing ratio of surface to volume.