Upconversion (UC) Er, Yb-CeO2 hollow spheres were successfully prepared using carbonaceous spheres as removable template via hydrothermal method for improving the efficiency of dye-sensitized solar cells (DSSCs). Light harvesting efficiency was enhanced 27% due to the upconversion effect, scattering effect and higher dye loading capacities. It is expected that the work provides a new optimization approach for CeO2 application in DSSCs.