The microscopic investigation of structural changes of bulk chalcogenide glasses and evaporated amorphous films by annealing and photoirradiation is carried out by the change of the ESR spectrum Mn doped as probe. The signal is found to change by the composition of the sample and by annealing. The change of the signal appears to be caused also by photoirradiation, but the reproducibility could not be established at the present stage. Although the present work is preliminary and a full understanding has not yet been achieved, the investigation of the change of the ESR signal is believed to be very useful in understanding the structural change from the microscopic point of view.