The advances in the studies of resonance laser-induced processes in heterogeneous systems are considered. Despite the advantages of adsorbed state at the interfaces, the attempts to implement isotope separation by direct processes of laser-induced desorption were not successful. Studies of different surface processes induced by IR laser radiation demonstrate a resonance character of the action, but the anticipated isotopic selectivity was never observed, apparently, because of rather quick energy exchange, decay or transfer to other species. Time-resolved spectroscopy and band shape analysis provide the data on the energy and phase relaxation of vibrational excitation. The energy transfer in the adsorbed layer occurs via resonance dipole–dipole interaction. The knowledge obtained enables us to propose recommendations for the choice of systems to achieve the isotopic selectivity.