Time-resolved photoluminescence measurement is done on glassy GeSe 2. The decay curve consists of a process whose decay time is about ∼0.3 ms and a faster process whose decay time is less than 1 μs. The decay time of the slower process becomes short with increasing excitation energy. The ratio between the slower process and the faster process increases with increasing excitation energy especially in the higher emission energy region. The relaxation process from the excited state just after the photon absorption to the trapped excited state is discussed.