On the basis of the glass network structure and spectroscopy information, the full-color-emitting borophosphate glasses doped/codoped with Eu2+ and Mn2+ ions were synthesized, and their photoluminescence (PL) properties were evaluated. The interaction of Mn2+–Mn2+ pairs shifts its emission to longer wavelength without a notable negative effect on the intensity in Mn2+-doped glasses. Depending on the small amount of B2O3 added, the Mn2+ ions suffer different surrounding environments giving three emission bands at 526, 597, and 638 nm, respectively. In codoped samples, the weak red emission resulting from the forbidden transition of Mn2+ could be enhanced by the energy transfer from Eu2+ because of the spectral overlap between the PL excitation spectrum of Mn2+ and the PL spectrum of Eu2+. The energy transfer process was confirmed by the luminescence spectra, transmittance spectra, and the calculation of energy transfer efficiency of the glasses. Meanwhile, the potential mechanism of energy transfer is evident to be dipole–dipole interaction. Finally, the Eu2+–Mn2+-codoped borophosphate glasses showed an adjustable full-color emission that could be regarded as a good candidate for ultraviolet light-emitting diode (LED) chip-based white LEDs.