Smart materials based on stimuli-fluorochromic π-conjugated solids (SFCSs) have aroused significant interest due to their versatile and exciting properties, leading to advanced applications. In this review, we highlight the recent developments in SFCS-based smart materials, expanding beyond organometallic compounds and light-responsive organic luminescent materials, with a discussion on the design strategies, exciting properties and stimuli-fluorochromic mechanisms along with their potential applications in the exciting fields of encryption, sensors, data storage, display, green printing, etc. The review comprehensively covers single-component and multi-component SFCSs as well as their stimuli-fluorochromic behaviors under external stimuli. We also provide insights into current achievements, limitations, and major challenges as well as future opportunities, aiming to inspire further investigation in this field in the near future. We expect this review to inspire more innovative research on SFCSs and their advanced applications so as to promote further development of smart materials and devices.