This monograph provides fundamental concepts utilized in infrared (IR) and Raman analysis of coatings as well as applications of attenuated total reflectance (ATR), reflection–absorption (RA), photo‐acoustic (PA), and IR/Raman imaging techniques. This choice of techniques is dictated by the fact that these techniques alone or their combination allow one to obtain a three‐dimensional molecular level representation of polymeric coatings, quantitative or semi‐quantitative analysis, surface/interfacial depth profiling, and determination of structure–property relationships in coatings. As a result, the effect of molecular level interactions/processes on macroscopic properties can be elucidated.