Laser‐induced sputtering from the (111) surface of BaF2was investigated under ultrahigh vacuum conditions, applying fluences well below the macroscopic damage threshold. Measurement of the wavelength‐dependent desorption of Ba+indicates that Ba+is emitted from two chemically different surroundings at the surface. For a fixed wavelength, the emission rates of Ba+and F+as functions of time show a distinct anticorrelation, confirming the existence of two different chemical states of the surface, and suggesting that the sputtering takes place layer by layer.