Rotationally resolved experiments on the NO/Pt(111) system explore the mechanisms of inelastic scattering and trapping/desorption. The rotational dynamics associated with these two regimes are markedly different. A neat supersonic NO beam is scattered at normal incidence from a Pt(111) crystal at 375–475 K. The non‐Boltzmann rotational population distribution of the scattered species exhibits considerable rotational excitation beyond the energy available from the incident beam. Thus, a surface vibration to rotational energy transfer mechanism must be operative. The accompanying rotational alignment data reveal that highly excited rotational states exhibit predominantly ‘‘cartwheel’’ motion. In contrast, rotationally excited molecules that desorb from a 553 K Pt(111) surface show a preference for ‘‘helicopter’’ motion. The opposite preferences for rotational alignment in the two dynamical regimes provide insight into the anisotropy of molecule–surface interactions.