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.

Surface functionalization is an interesting way to elaborate new smart materials. In this work, a two-step surface modification, based on pulsed plasma polymerization, was used to design functional surfaces able to react by Diels−Alder reaction (a diene−dienophile cycloaddition). The reactivity of furan-functionalized (diene) surfaces with a maleimide-derivative (dienophile) was studied. The determination of the rate constants led to the determination of the activation energy, the enthalpy of activation, and the entropy of activation. These results were then compared to those obtained in solution. For the first time, it was possible to understand the role played by molecule confinement (close to the surface) on the Diels−Alder reactivity.