Upconversion/semiconductor submicron hollow spheres composed of inner NaxGdFyOz:Yb/Er shell and outer TiO2 shell (denoted NaxGdFyOz:Yb/Er@TiO2) were, for the first time, crafted by exploiting colloidal carbon spheres as the scaffold. The hollow spheres were then incorporated into the TiO2 nanoparticle film photoanode to yield dye-sensitized solar cells (DSSCs) with improved performance. The implementation of NaxGdFyOz:Yb/Er@TiO2 hollow spheres in DSSCs imparted the light trapping due to the light scattering from submicron hollow spheres, and the harvesting of near infrared solar photons by the upconversion material (i.e., dual functionalities), thereby resulting in an increased short-circuit current density Jsc, and thus an improved power conversion efficiency PCE. The electrochemical impedance spectroscopy measurements were performed to scrutinize the interfacial charge transfer characteristics of DSSCs. The measurements revealed that when NaxGdFyOz:Yb/Er hollow spheres without the deposition of TiO2 shell were integrated in the photoanode, a high charge transfer resistance was found. In stark contrast, the judicious decoration of NaxGdFyOz:Yb/Er hollow spheres with a thin layer of TiO2 shell markedly improved the contact between the resulting NaxGdFyOz:Yb/Er@TiO2 shell/shell hollow spheres and the TiO2 nanoparticle film photoanode, leading to a much decreased charge transfer resistance. Taken together, compared to the PCE of 6.81% for the pristine device, the DSSC assembled with the introduction of 8 wt% NaxGdFyOz:Yb/Er@TiO2 hollow spheres in the photoanode exhibited an optimal PCE of 7.58% and a maximum short-circuit current density Jsc of 18.72 mA cm-2 under AM 1.5G one sun illumination, corresponding to 11.31% performance enhancement. As such, the implementation of upconversion submicron hollow materials in photoanode may stand out as an intriguing strategy to improve the device performance of DSSCs.