In the 1980s, Helmuth Möhwald studied lipid monolayers at the air/water interface to understand the thermodynamically characterized phases at the molecular level. In collaboration with Jens Als-Nielsen, X-ray reflectometry was used and further developed to determine the electron density profile perpendicular to the water surface. Using a slab model, parameters such as thickness and density of the individual molecular regions, as well as the roughness of the individual interfaces, were determined. Later, X-ray and neutron reflectometry helped to understand the coverage and conformation of anchored and adsorbed polymers. Nowadays, they resolve molecular properties in emerging topics such as liquid metals and ionic liquids. Much is still to be learned about buried interfaces (e.g., liquid/liquid interfaces). In this Article, a historical and theoretical background of X-ray reflectivity is given, recent developments of X-ray and neutron reflectometry for polymers at interfaces and thin layers are highlighted, and emerging research topics involving these techniques are emphasized.