Metastable intermolecular composite (MIC) Al/Bi2O3 has good features of high combustion efficiency, fast energy releasing rate, high pressure pulse, good safety performance and being environment friendly. It shows good application prospects in pyrotechnics, explosives and propellants, etc. In this review, reaction mechanisms and models, preparation and applications of the metastable intermolecular composite Al/Bi2O3 are summarized. First, various theories and models which were used to explain the reaction mechanism of thermites are introduced and compared. The models of the CJ (Chapman-Jouguet) detonation and thermal equilibrium which could interpret and simulate output pressure of Al/Bi2O3 reasonably are discussed in detail. Second, the preparing methods of Bi2O3 and Al/Bi2O3 are summarized. By using different preparing processes, the morphologies, microstructures and combustion performances of composites could be regulated. Meanwhile, the effects of reactants particle size and various additives in preparing Al/Bi2O3 on its combustion performances are analyzed. Furthermore, a brief introduction of the application research is also presented. Finally, we proposed prospects about the metastable intermolecular composite Al/Bi2O3