Negative ion-beam-induced luminescence (IBIL) measurements of a pure LiF crystal using 20keY H-are performed to monitor the formation and annihilation of luminescence centers during ion irradiation.Several emission bands are observed in the IBIL spectra and the evolvement mechanisms of the corresponding centers are identified.The difference between the IBIL measurements using positive ions and negative ions is that the intensities of luminescence centers can reach the maxima at lower fluences under negative-ion irradiation due to free charge accumulation.