We have studied the effect of γ-ray irradiation on optical absorption, emission and decay characteristics of RE3+ (RE = Sm, Eu and Dy)-doped fluorophosphate glasses. Electron paramagnetic resonance (EPR) study confirms the POHC and PO3 EC defects induced in glasses by the γ-irradiation. The presence of induced defect centers significantly affects the optical and emission properties. The optical band gap values of the studied systems increased after the γ-ray irradiation. The phonon energy and electron–phonon coupling strength of Eu3+-doped fluorophosphate glass were determined from the phonon sideband analysis. The emission intensity of the RE3+ ions increased significantly after the γ-ray irradiation. The intensity parameter, R is the ratio of the intensities of the 5D0 → 7F2/5D0 → 7F1 transitions of Eu3+ ion and Y/B intensity parameter is the ratio of intensities of the 4F9/2 → 6H13∕2/4F9/2 → 6H15/2 transitions of Dy3+ ion reveal that the local environment around the RE3+ ion changed after the γ-ray irradiation in the present system. The lifetime of excited states of RE3+ ions decreased after the γ-ray irradiation due to the formation of defects induced by the γ-ray irradiation. The CIE color coordinates were determined before and after the γ-ray irradiation for the Dy3+-doped glass system.