The influence of the deposition temperature on the grain size of polycrystalline lithium fluoride (LiF) thin films is studied using a mathematical morphology method. On atomic force microscopy images of the LiF surface, the grain sizes and shapes are determined by applying the watershed technique, together with a shape factor algorithm. Also, the domain size of the film structure, determined by an X-ray diffraction data analysis, is compared and correlated with the mean grain size as a function of the deposition temperature. In both cases a linear increase with temperature and a very good agreement among the two structural parameters (grain and domain size) was found.