Abstract Time resolved emission spectra of Mn 2+ in ZnS nanocrystals were studied. Two split-pair bands at high- and low-energy sides of the peak position of the conventional Mn 2+ emission band were observed at short delay times. They emerge gradually into the conventional emission band of Mn 2+. These two bands were assumed to be hot luminescence which comes from the vibronic transitions from the vibrational states of the excited state of Mn 2+ to its ground state. The population and energy relaxation times of hot electrons were deduced.