In this work, the Tb3+/Eu3+ co-doped 30SrO-10MgO-50SiO2-5TiO2-5B2O3-1Tb2O3-xEu2O3 (x = 0-2.5 mol% at 0.5 intervals) glasses were prepared by the melt-quenching method, and the single-phase Sr2MgSi2O7 glass-ceramics were obtained after heat treatment. The structural and fluorescence performance of the glasses and glass-ceramics were examined using DSC, XRD, SEM, FTIR, and photoluminescence spectra, and the energy transfer process between Tb3+ and Eu3+ was systematically investigated. With increasing Eu2O3 contents, the thermal stability of the glasses is enhanced and the density of both the glasses and the glass-ceramics rises. The XRD and SEM results reveal the precipitation of the irregular spherical Sr2MgSi2O7 microcrystals with a grain size roughly within 0.5-1 μm. Under 376 nm excitation, the overall emission intensity and lifetime of Eu3+ ions increase with increasing Eu2O3 contents, and the energy transfer efficiency reaches 58.74% from 31.07%. According to the Dexter model, the energy transfer process between the Tb3+ and Eu3+ is dominated by the quadrupole-quadrupole interactions. By varying the Eu2O3 contents, all the glass-ceramics exhibit higher color purity (82.06-96.27%), and their chromaticity coordinates shift from yellowish green towards reddish orange, which is potentially promising for w-LEDs.