In this article, we report the luminescent properties and energy transfer behavior of Tb and Eu in aluminosilicate and zinc silicate glasses. Both glass systems exhibit a combination of blue, green, and red emissions. The optical absorption spectra provide an evidence of the reduction reaction of Eu3+ ions in aluminosilicate glasses and it proves that the aluminosilicate glasses may be more promising for producing white light due to the existing blue light emission of Eu2+ ions. The emission and lifetime measurements reveal the energy transfer is from Tb3+ (5D4) to Eu3+ (5D1) by the quadrupole–quadrupole interaction between these two ions. The calculated energy transfer efficiency is up to 32.1% in zinc silicate glasses.