A series of copper species, Tb3+, Mn2+ single- and co-doped oxyfluoride glasses were synthesized by a melt-quenching method. The photoluminescence properties of the glasses containing copper species were demonstrated. Results indicate that the blue-green emission band peaking at 440nm was observed, which was ascribed to the photoluminescence of Cu+ ions rather than the emissions of Cu2+ cations or Cu nano-particles (Cu NPs) induced by local field effect (LFE) enhancement through surface plasmon resonance (SPR). The interaction mechanisms between Cu+ and Tb3+/Mn2+ have been systematically investigated, and significant enhancement of Cu+ emission and the energy-transfer (ET) efficiencies of Cu+Tb3+ and Cu+Mn2+ were observed in glasses doped with SnO reducing agent. Furthermore, a wide-range-tunable emission and ideal white-light fluorescence were realized in Cu+/Tb3+/Mn2+-coactivated glasses by utilization of Cu+ cations as dual ET contributors from deep-UV-source to multiactivators. Our research further extends the understanding of the interactions between Cu+ and Tb3+/Mn2+ in amorphous materials.