In order to enhance the photovoltaic performance of dye-sensitized solar cell (DSSC), a novel design is demonstrated by introducing rare-earth compound europium ion doped yttrium fluoride (YF3:Eu31) in TiO2 film in the DSSC. As a conversion luminescence medium, YF3:Eu31 transfers ultraviolet light to visible light via down-conversion, and increases incident harvest and photocurrent of DSSC. As a p-Type dopant, Eu31 elevates the Fermi level of TiO2 film and thus heightens photovoltage of the DSSC. The conversion luminescence and p-Type doping effect are demonstrated by photoluminescence spectra and Mott-Schottky plots. When the ratio of YF3:Eu31/TiO2 in the doping layer is optimized as 5 wt.%, the light-To-electric energy conversion efficiency of the DSSC reaches 7.74%, which is increased by 32% compared to that of the DSSC without YF3:Eu31 doping. Double functions of doped rare-earth compound provide a new route for enhancing the photovoltaic performance of solar cells.