Eu3+ and Tb3+ ions singly activated Gd2O2S hollow spheres have been successfully synthesized via solvothermal method by using Gd (NO3)3, Eu (NO3)3, Tb (NO3)3 and thiourea as raw materials. Detailed characterization of the as-prepared samples were obtained by X-ray diffractometry (XRD), field emission scanning electron microscopy (FE-SEM), transmission electronic microscope (TEM) and photoluminescence (PL) spectroscopy. The results demonstrate that at 220 oC for 24 h, the molar ratio of thiourea/Gd3+ has no significant impact on the phase composition of Gd2O2S products. With the reaction time increased from 6 h to 24 h, the morphology of Gd2O2S samples changed from ellipsoidal to near-spheroidal structure, but still remained hollow structure. PL results show that the strongest emission peaks for Gd2O2S:Eu3+ and Gd2O2S:Tb3+ samples were centered at 625 nm and 545 nm, corresponding to the 5D0→7F2 transition of Eu3+ ions and 5D4→7F5 transition of Tb3+ ions, respectively. The quenching concentrations for Eu3+ and Tb3+ ions were 12% and 6%, which can be attributed to the exchange interaction for Eu3+ and Tb3+ ions, respectively.