Thermochromic materials (TCMs) reversibly change their color or near‐infrared response with temperature, and a growing literature treats them as passive self‐regulating components in energy‐efficient buildings, wearable diagnostics, cold‐chain monitoring, and adaptive optical systems. Most existing reviews, however, are descriptive surveys that catalog mechanisms and processing routes without testing them against one another or against the realities of deployment. The present review takes a deliberately critical and comparative stance. Rather than an inventory of eight unconnected switching effects, the underlying physics is grouped into three families, namely, electronic and structural transitions in solids, molecular reconfiguration in discrete species, and supramolecular ordering in mesophases, and a common set of performance descriptors lets dissimilar materials be compared on an equal footing. The platforms are then assessed against those descriptors, with emphasis on the doping trade‐offs that govern the transition temperature of vanadium dioxide, the toxicity and regulation that render mercury‐based ionic conductors effectively unusable, and the photodegradation and cycling fatigue that constrain organic leuco‐dye and spiro systems. Synthesis, microencapsulation, and coating are treated as a single manufacturing chain and judged on scalability, reproducibility, cost, and technology readiness, since these factors, not laboratory optical contrast, ultimately decide whether a technology reaches the market. Durability is analyzed through combined ultraviolet, thermal, oxidative, and hydrolytic stress, and through the reproducibility gap left by nonstandard accelerated‐aging protocols. Deployment is framed within intelligent engineering systems, where TCMs act as passive actuators alongside sensor networks, building‐management systems, and digital‐twin models. The argument is supported by eight original schemes and eight comparative tables. We conclude that the principal barriers to adoption are no longer the questions of scientific novelty but of durability, cost at scale, standardization, and system‐level integration, and we map the research directions most likely to close these gaps.