AgNO3/EuF3/YbF3 tri-doped oxyfluoride glass was prepared by a melt-quenching method, in which a high-efficient broadband spectral modification can be realized due to the simultaneous energy-transfer processes of Eu3+ -> Yb3+, molecular-like Ag ( ML-Ag) clusters -> Yb3+, and ML-Ag clusters -> Eu3+ -> Yb3+. The spectral measurements indicated that besides the F-center brought by the fluorides, the formation of the ML-Ag clusters and the evolution of silver species within the glass matrix were also closely related to the introduction of Eu3+ and Yb3+ ions and which in return greatly affected the luminescence properties of these rare-earth ions. As the UV-visible irradiation in the wavelength region of 250-600 nm can be efficiently converted into near-infrared emission around 1000 nm in the AgNO3/EuF3/YbF3 tri-doped glass, which thus has promising application in enhancing the photovoltaic conversion efficiency of the silicon solar cell.