Benefits of cost effective, light weight, coloring, easier processing, DSSCs (dye-sensitized solar cells) are potential substitutes aimed at conversion of solar energy, balancing to the well-established silicon solar photovoltaics. In the present study, CeO2:Er3+/Yb3+ sub-micrometer size upconversion particles prepared through conventional hydrothermal process. Upconversion emission peaks at similar to 652-700 nm along with similar to 520-550 nm are witnessed by excite 980 nm laser light. The light scattering performance is achieved by use of CeO2:Er3+/Yb3+ layer over TiO2 film. Insertion of CeO2:Er3+/Yb3+ on the top of TiO2 film is further treated with LiI contained acetonitrile solution. Cost effective, platinum-free counter electrode (CE) made with Tin sulfide (SnS), carbon and its composite are sandwiched with surface treated photoelectrode for DSSCs fabrication. The enhanced power conversion efficiency (PCE) 9.52% for LiI treated CeO2:Er3+/Yb3+ based DSSC is witnessed with composite CE is higher than Pt based DSSC (8.32%).