The Next Frontier in Perovskite Stability: Operando Smart‐Responsive Materials Driving the Next Revolution

Perovskite solar cells (PSCs) have achieved remarkable progress in the past decade, but their long-term stability remains a major obstacle to commercialization. The stability of optoelectronic devices under real operating conditions is particularly critical, as ion migration induced by external factors such as light, heat, and humidity is a key cause of material and device degradation. Recently, the introduction of stimuli-responsive materials into perovskite systems has endowed them with multifunctionality and operando stabilization, potentially transforming harmful external stimuli into beneficial factors for enhanced performance. Operando-responsive systems can dynamically adjust their physicochemical state according to external stimuli such as illumination, temperature, or humidity, thereby providing adaptive protection during device operation. Therefore, developing such systems has become a cutting-edge research direction for improving stability under harsh conditions. Such an approach not only provides a new pathway to overcome intrinsic instability issues but also expands the functional boundaries of perovskite materials, extending them beyond traditional photovoltaic applications. This review systematically summarizes recent advances in smart responsive strategies for PSCs, focusing on their underlying mechanisms and exploring how operando molecular dynamics redefine stability engineering. Furthermore, we outline the key challenges in developing truly operando adaptive smart self-regulating PSCs and propose future directions for development.