The equivalent or hetero-valent substitution of ions in a host is an efficient method for stimulating photoluminescence tuning to optimize the photoluminescence performances in phosphor materials. The study of Bi3+/Mn2+ co-doped oxides is currently of interest to solve the lack of red-orange components in commercials phosphor-converted white light-emitting diodes. In this article, we designed KMgF3 perovskite glass-ceramics that the Mg cation substitute by Bi3+/Mn2+, based on the radius and coordination of the cations and heat-treatment through solid-state microwave reaction. The photoluminescence (PL) determined and were systematically characterized. In contrast, the doped Bi3+/Mn2+ ions can be effectively doped in the KMgF3 in the glassy matrix. The prepared glass and glass-ceramics co-doped Bi3+/Mn2+ glasses exhibit intense tunable emitting color between blue and orange-red regions due to an efficient energy transfer from Bi3+ to Mn2+.