The time-resolved photoluminescence (TRPL) of red HgI 2 single crystal has been measured to determine the carrier lifetimes and to reveal the energy relaxation of excitons. Sharp near-bandgap luminescence lines due to free and bound excitons are observed at 530 nm, and a broad luminescence band appears at 630 nm at low temperatures. TRPL experiments of the near-bandgap luminescence have revealed that the luminescence comprise fast (30 to 200 ps) and slow (100 to 400 ps) decay components, showing several relaxation processes in free and bound exciton annihilation. TRPL of the broad band at 630 nm has shown that the luminescence is ascribed to the radiative recombination of donor-acceptor (DA) pairs.