Stimuli‐responsive materials have properties that depend on the environment in which they are used. In most cases, the material itself is formulated to react to the corresponding stimulus. However, many phenomena occur at the surface of the material. In this context, the design and the investigation of the reactivity of stimuli‐responsive surfaces are particularly interesting. More precisely, this review focuses on functional coatings that react via Diels–Alder (DA) chemistry, a thermoreversible reaction between a diene and a dienophile. According to the nature of the substrate, these coatings are mainly based on self‐assembled monolayers or silane assemblies, on polydopamine derivatives, or on polymer thin films deposited by vapor‐phase processes including plasma polymerization. The different works discussed here show that interfacial thermoreversible reactions occur between a DA‐functionalized surface and a DA reactant in solution but also between two solid substrates are possible. The direct cycloaddition is always described in the cited papers but the reversibility of the reaction is less discussed. The latter however remains very challenging for smart applications in material science. This review reports on the fabrication of functional surfaces with thermoreversible properties and the understanding of their reactivity via the Diels–Alder reaction. Based on various functionalization processes, the designed surfaces have various physico‐chemical properties, leading to different Diels–Alder reactivity. The direct cycloaddition is always described in the cited papers but the reversibility of the reaction is less discussed.