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The Eu2+and Dy3+co-doped luminescence high silica glass was prepared by combining porous glass preparation and sintering process. The emission spectra and excitation spectra of luminescence glasses were measured. With the excitation of ultraviolet (UV) wavelength of 365nm, there were two emission bands with central wavelength 480nm and 573nm in spectra of samples which presented the near white light luminescence. The energy transfer process from Dy3+to Eu2+and concentration quench process of Eu2+in samples were demonstrated by comparing the relative spectral intensity of emission spectra and excitation spectra. This type of glass might be an adoptable candidate for white LED through an appropriate UV chip excitation.