•Current review on Self-healing polymers based on Diels-Alder cycloaddition.•Discussing healing thermodynamics for physical and chemical changes during healing.•Deeper insight on use of advanced analytical/spectroscopic/modelling techniques.•Use of multifunctional healing mechanisms for advanced engineering applications.•Future scope of DA polymers based on better commerciality and green chemistry. The ability of artificial materials to be healed efficiently, mimicking the living organisms, exhibits a great deal of potential advantages that can revolutionise the operation and maintenance of materials used in various applications. Such self-healable smart materials have been extensively researched in the last few decades, leading to the development of different physical and chemical synthesis approaches. Among these methods, chemical techniques based on reversible cycloadditions or disulfide bonding provide obvious advantages in terms of repeatability, which holds prime importance in determining the commerciality of the healing approach. This review compiles the recent advances in the field of self-healing polymers where the healing ability is introduced by reversible cycloaddition reactions while focusing mainly on the Diels-Alder (DA) reaction. DA is a 4 + 2 cycloaddition reaction where diene and dienophile pairs are used to fabricate thermally reversible crosslinked networks. These covalent bonds provide the necessary reversibility to the healing matrix and impart the desired strength to the polymeric material. There is a considerable body of recent literature where DA bonding has been employed either on its own or along with other healing mechanisms to impart self-healing to polymers. However, lack of a systematic review discussing these works makes it difficult for a beginner to cope with advancements in this field. Most early studies have focused on the healing stimuli and efficiency of healing in polymers but with this review, we would like to explore the healing thermodynamics governing the rupture–repair process in DA polymers along with the use of advanced spectroscopic techniques to study them and their applicability in thermosets, epoxy resins, biopolymers, and polymer nanocomposites. Novel applications for such advanced functional polymers, multifunctional healable polymers, and the outlook for future research, opportunities and challenges in the area are also discussed.