Bi3+–Ln3+ (Ln = Dy, Er, Ho, Eu, and Sm) co-doped YVO4 phosphors are proposed as UV-absorbing luminescent converter candidate to enhance the power conversion efficiency and photochemical stability of dye-sensitized solar cells (DSSCs). The phosphors can efficiently convert UV photons in a broad range from 250 to 400 nm into visible emissions, which can be absorbed by DSSCs. Efficient broadband down-conversion UV light into near-infrared emission around 1000 nm was achieved in the YVO4:Bi3+,Yb3+ phosphors. The energy transfer from V5+–Bi3+ charge-transfer state to Yb3+ was shown to be a cooperative down-conversion type by the luminescence spectra, energy transfer efficiency, and luminescence decay curves. The YVO4:Bi3+,Yb3+ phosphors are promising for boosting the efficiency of crystalline silicon solar cells by down-converting the UV part of the solar spectrum to near-infrared photons with a twofold increase in the photon number. This research may open up promising new perspectives for designing novel luminescent materials for photovoltaic cells with high efficiency.