The single crystals LiF with copper impurity were grown by Czochralski method. The concentrations of Cu in the crystals were 0,0004-0,002%. In order to determine a copper valence impurity, measurements of the ESR, emission, excitation and absorption spectra were performed. We found emission peak at 410 nm and excitation peak at 250 nm. In agreement with reference, these peaks point to presence of Cu + in our samples. The mechanisms of capture and recombination providing process of thermoluminescence were recognized.