Studies on the following were reviewed: (1) the structure of spiropyrans and spirooxazines (two kinds of spiro compounds) under external stimuli and (2) the construction and applications of composite systems based on fluorescence resonance energy transfer (FRET) with fluorescent materials. When treated with different stimuli (light, acids and bases, solvents, metal ions, temperature, redox potential, and so on), spiropyrans/spirooxazines undergo transformations between the ring-closed form (SP), the ring-opened merocyanine (MC) form, and the protonated ring-opened form (MCH). This is due to the breakage of the spiro C-O bond and the protonation of MC, along with a color change. Various novel, multifunctional materials based on photochromic spiropyrans and spirooxazines have been successfully developed because of the vastly differently physiochemical properties posssed by the SP, MC and MCH forms. Among the three different structural forms, the MC form has been studied most extensively. The MC form not only gives complexes with various inorganic particles, biological molecules, and organic chemicals but also acts as the energy acceptor (of energy from fluorescent molecules) during energy transfer processes that take place under proper conditions. Furthermore, spiropyran and spirooxazine compounds exhibit reversible physicochemical property changes under proper stimuli; this provides more advantages compared with other photochromic compounds. Additionally, the molecular structures of spiropyrans and spirooxazines can be easily modified and extended, so better compounds can be obtained to expand the scope of already known applications. Described in detail are: (1) the structural properties of spiropyrans and spirooxazines and related photochromic mechanisms; (2) composite systems based on spiropyrans and spirooxazines, and (3) fluorescent materials which have potential applications in sensing, probing, and a variety of optical elements.