Trap level spectroscopic investigations have been carried out on LiF doped (separately) with uranium and americium using EPR, TSL and TSL-spectral techniques. These studies, apart from obtaining trap parameters-trap depths and frequency factors-helped in elucidating the processes that occur in electron and hole trapping and their subsequent recombination on thermal stimulation. In the uranium-doped sample the electron trapping by U⁶⁺ complexes (UO_6-)^6- and (UO₅F)^5- at (LiF_6-)^5- sites and subsequent electron-hole recombination at U⁶⁺ has been identified as the predominant mode of TSL. In ²⁴¹Am-doped sample americium has been found to be stabilised in the divalent state. Whereas in the high-temperature region F-centre production and Am²⁺ to or from Am³⁺ were found to be the dominant modes of electron and hole trapping, respectively, in the region below room temperature Am²⁺ to or from Am⁺ and production of U₃ centres (hydrogen atoms at F^- sites) were found to be the dominant modes of electron and hole trapping, respectively. In both high-temperature and sub-room-temperature regions electron-hole recombination results in the creation of electronically excited Am²⁺ resulting in the luminescence of Am²⁺ on thermal stimulation.