The effect of optical radiation during the phase transition from the amorphous to the crystalline state of matter was investigated for the first time. The results were obtained on nanoscale films of (LiF)x(Li2B4O7)1‐x compositions by sputtering on cold Ni substrates. The starting materials for films were chosen due to their wide use for tissue‐equivalent ionizing radiation dosimetry. It is shown that the detected thermoluminescence effect is sensitive to the thickness of the films. The paper compares the results of these studies with the study of the thermoluminescence characteristics of films irradiated by an M‐30 microtron with bremsstrahlung radiation with a maximum energy of 6 MeV. The absorbed radiation dose was 1 kGy. Differences in the luminescence characteristics of irradiated and nonirradiated films were revealed. The nature of the demonstrated structural–optical effect is discussed.