In the present review, we focused on the fundamental concepts of hydrogels—classification, the polymers involved, synthesis methods, types of hydrogels, properties, and applications of the hydrogel. Hydrogels can be synthesized from natural polymers, synthetic polymers, polymerizable synthetic monomers, and a combination of natural and synthetic polymers. Synthesis of hydrogels involves physical, chemical, and hybrid bonding. The bonding is formed via different routes, such as solution casting, solution mixing, bulk polymerization, free radical mechanism, radiation method, and interpenetrating network formation. The synthesized hydrogels have significant properties, such as mechanical strength, biocompatibility, biodegradability, swellability, and stimuli sensitivity. These properties are substantial for electrochemical and biomedical applications. Furthermore, this review emphasizes flexible and self-healable hydrogels as electrolytes for energy storage and energy conversion applications. Insufficient adhesiveness (less interfacial interaction) between electrodes and electrolytes and mechanical strength pose serious challenges, such as delamination of the supercapacitors, batteries, and solar cells. Owing to smart and aqueous hydrogels, robust mechanical strength, adhesiveness, stretchability, strain sensitivity, and self-healability are the critical factors that can identify the reliability and robustness of the energy storage and conversion devices. These devices are highly efficient and convenient for smart, light-weight, foldable electronics and modern pollution-free transportation in the current decade.