An energy transfer process from Ce3+ to Tb3+ ions was successfully achieved in a Li2SO4–Al2(SO4)3 mixed‐sulphate system. A wet‐chemical synthesis was employed to prepare the Li2SO4–Al2(SO4)3 system by doping Ce3+ and Tb3+ ions individually as well as collectively. The phases were identified using X‐ray diffraction studies. The as‐prepared samples were characterized by FT‐IR and photoluminescence measurements. Green‐light emission was exhibited by Ce3+, Tb3+ co‐doped Li2SO4–Al2(SO4)3 system, thus, indicating its potential as a material for display devices or in the lamp industry.