Photoluminescence (PL), photostimulated luminescence (PSL), thermally stimulated luminescence (TSL) and electron paramagnetic resonance (EPR) studies were carried out on LiYF₄:U⁴⁺ and pure LiYF 4crystals. The P Land EPR investigations have identi7ed the presence of Eu³⁺,Tb³⁺ and Gd³⁺ions in both of these crystals possibly due to their existence in the starting materials. The luminescence observed during afterglow, PS Land TS Lrevealed that emission occurs at wavelength positions 382, 413, 437 and 544 nm, which are characteristic of Tb³⁺ions. The present investigations using PS Land TS Lin combination with P Lstudies before and after gamma irradiation have revealed that selective energy transfer to Tb3+ions occurs during electron–hole recombination processes like PS Land TS L. Even though other luminescent ions (U⁴⁺and Eu³⁺)are present in the system and U⁴⁺=U³⁺ions are participating in electron capture/release processes, the selective energy transfer results in Tb³⁺ions acting as luminescence centers