In this paper, the spectral modulation by the quantum-cutting luminescence of Er3+Yb3+ ion-pairs in nanophase oxyfluoride vitroceramics is studied. We obtained X-ray diffraction spectra, surface topographies, excitation, absorption, and luminescence spectra of Er3+Yb3+ nanophase oxyfluoride vitroceramics, and compared them with the corresponding parameters of a Tb3+Yb3+-codoped sample. We find that the 652.0 nm wavelength red luminescence intensity is enhanced by the factors of 680.85 and 303.80 for (A) Er(1%)Yb(8.0%)∶FOV and (B) Er(0.5%)Yb(3.0%)∶FOV, respectively, when they are excited by 378 nm light than when they are excited by 522 nm light. It is also found that the 652.0 nm red luminescence intensity is enhanced 491.05 and 184.12 times for (A) Er(1%)Yb(8.0%)∶FOV and (B) Er(0.5%)Yb(3.0%)∶FOV than (C) Er(0.5%)∶FOV when they are both being excited by 378 nm light. the results show that the {978.0 and 1 012.0 nm} infrared luminescence intensities of (A) Er(1%)Yb(8.0%)∶FOV and (B) Er(0.5%)Yb(3.0%)∶FOV are {58.00 and 293.62} and {25.11 and 67.50} times, respectively, larger than the corresponding ones of (C) Er(0.5%)∶FOV when both excited with 378 nm light. And further, the intensities of the 378.5 nm excitation peak of (A) Er(1%)Yb(8.0%)∶FOV and (B) Er(0.5%)Yb(3.0%)∶FOV are about 606.02 time and 199.83 times, respectively, larger than (C) Er(0.5%)∶FOV when 652.0 nm luminescence wavelength is selected as the fluorescence receiving wavelength to measure the visible excitation spectra in the range of 250～628 nm. Meanwhile, we also find that the first-order quantum-cutting infrared 1 012 or 978 nm luminescence intensities of (A) Er(1%)Yb(8.0%)∶FOV and (B) Er(0.5%)Yb(3.0%)∶FOV are about 101.38 and 29.19 times larger than the second-order quantum-cutting infrared 976 nm luminescence intensity of (D) Tb(0.7%)Yb(5.0%)∶FOV. To the best of our knowledge, present quantum-cutting obtained in our study is the most intense quantum-cutting reported to date. Therefore, we believe that present first-order quantum-cutting luminescence of Er3+Yb3+-codoped oxyfluoride vitroceramics may be intense for the material’s use as a quantum-cutting layer to enhance the photovoltaic conversion efficiency of crystal silicon solar cell. The results can facilitate the probing of next-generation environmentally friendly spectral-modulation solar cells, which are currently the focus of global attention.