The desorption of fluorine from barium fluoride thin films deposited on silicon substrate has been observed due to the incidence of electron beam during Auger electron spectroscopic (AES) studies. Slow electron energy loss spectroscopy (SEELS) has been employed to observe changes in core levels and color center formation. The desorption cross section for fluorine and the critical electron beam dose necessary to initiate electron‐stimulated desorption have been estimated. The results are envisaged to provide information to investigators performing AES on such materials to choose parameters so as to eliminate or reduce beam damages. Since the desorption of fluorine results in metalliclike barium on the surface, it can also be a technique to deposit clean Ba layers on cathode materials to achieve work‐function reduction.