Well dispersed and homogeneous Y2O2S:Sm3+ hollow submicrospheres were successfully achieved by a template- free solvothermal method combining with a postcalcining process. The crystalstructure and particle morphology were investigated by the X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectra, scanning and transmission electron microscopy (SEM and TEM), respectively. A possible growth mechanism was proposed to reveal the formation process. Luminescence properties of the Y202S:Sm3+ long-lasting phosphor were an- alyzed by measuring the excitation spectra, emission spectra, afterglow decay curve and thermoluminescence curve. The excitation spectra indicated that the phosphor could be excited effectively by the ultraviolet-light emitting diode (UV-LED) or blue LED, and the emission spectra showed that the phosphor could emit red light from 600 to 650 nm.