We present results on simultaneous nanostructuring and optical activation of lithium fluoride crystals by 800eV off-normal Ar+ sputtering at different ion doses. The samples were studied by atomic force microscopy and optical spectroscopy. After ion irradiation smoothening of the initial random roughness is achieved and well-defined self-organized ripple structures appear, having a mean periodicity of 30nm and a mean height of 3nm. The simultaneous optical activation of the irradiated samples is due to the stable formation of electronic defects with intense photoluminescence in the visible spectral range.