The MgAl2O4:Eu2+, Dy3+ nanophosphors with different particle sizes have been synthesized through a simple and inexpensive precipitate approach followed by a post-annealing process. The structure and morphology of the phosphor are characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). According to XRD and TEM results, the particle size of MgAl2O4:Eu2+, Dy3+ could be controlled via changing the ratio of MgSO4/Al2O3, and the obtained samples possess regular morphology. The afterglow properties of MgAl2O4:Eu2+, Dy3+ nanophosphors as a function of particle sizes are investigated by afterglow decay curves. Compared with the bulk phosphor, the nanophosphors exhibit longer afterglow time and higher initial afterglow intensity. In nanophosphors, there exist numerous defects on their surfaces due to the large surface to volume ratio, which generally act as luminescent killers, while some of which, however, can probably act as traps beneficial for the generation of afterglow. In the nanosized MgAl2O4:Eu2+, Dy3+ phosphor, the thermoluminescence results indeed indicate the existence of more traps which are introduced due to the large surface to volume ratio of nanoparticles and that the high temperature sintering process contributes to the longer afterglow in the nanophosphors.