Polyatomic ion-surface interactions are relevant to technological applications as diverse as the preparation of new electronic materials and biological mass spectrometry. These applications encompass secondaryion mass spectrometry with atomic, molecular, or cluster projectiles; reactive scattering for surface analysis; surface-induced dissociation for the structural analysis of molecular and cluster ions; surface modification by molecular ions, cluster ions, or plasmas; matrix isolation for spectroscopic analysis of unique ions; laser-surface interactions; electron-stimulated desorption; and molecular beam-surface interactions. Workers in this field come from condensed matter physics, mass spectrometry, materials science, physical chemistry, analytical chemistry, electrical engineering, and biomaterials. Current advances in fundamental knowledge of polyatomic ion-surface interactions grow from several decades of work on atomic ion-surface interactions in secondary-ion mass spectrometry, ion scattering for surface and bulk analysis, surface modification, electron emission, and charge transfer. The study of di-and triatomic ion scattering off clean metal surfaces also preceded much of the current studies of larger ions.