A series of Dy3+/Eu3+ single- and co-doped calcium borosilicate luminescent glasses were prepared by the conventional high temperature melt-quenching method. A compact glass structure is obtained by the addition of Dy3+/Eu3+ ions, which is verified by the physical properties of synthetic glasses. As network modifiers, Dy3+/Eu3+ fill in the interspaces of glass network and contribute to the conversion of [BO3] to [BO4]. Dy3+/Eu3+ co-doped calcium borosilicate glasses can emit white light, which consists of blue, yellow, and red light under 387 nm excitation. The emission spectra and decay curves of the white-emitting glasses have proved the existence of energy transfer. The average lifetime of Dy(3+ )decreases from 0.251 to 0.165 ms with the increasing Eu3+ concentration. Changing rare earth ions concentration, CIE color coordinates of Dy3+/Eu3+ co-doped glass shifts from cyan to white with increasing excitation wavelength. A white-light emission is obtained when the concentration of Dy3+ and Eu3+ equals to 4% and 2%, respectively. Moreover, the Dy3+/Eu3+ co-doped calcium borosilicate glass shows high-thermal stability and it may be applicable for high-quality white LEDs based on high power near ultraviolet (n-UV) LED chip in the future.