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Utilizing the pyrolysis reaction of endothermic hydrocarbon fuels to provide thermal protection for hypersonic vehicles is a feasible approach. The introduction of catalysts or cracking-initiating additives could promote hydrocarbon fuel cracking and increase the reaction heat sink. Catalysts such as ZSM-5 zeolite, Al2O3, and precious metals were commonly used for hydrocarbon fuel cracking. By optimizing their pore structure and acidity, their catalytic cracking performance can be effectively improved. These catalysts can function not only as catalytic coatings but also be dispersed in the fuel to act via quasi-homogeneous catalytic cracking. Additionally, small-molecule and macromolecular additives could crack at lower temperatures to generate active free radicals, thereby initiating the cracking of hydrocarbons and increasing the reaction heat sink. Under the conditions of a reaction temperature of 650–750 °C, a pressure of 3–5.5 MPa, and a fuel flow rate of 1 g/s, quasi-homogeneous catalysts can enhance the heat sink of hydrocarbon fuel cracking by 5–21%, while cracking-initiating additives can enhance it by 5.6–8.6%. Therefore, based on the different action modes of catalysts or additives, this review summarizes the recent research on improving the cracking of endothermic hydrocarbons from three aspects: coating catalysts, quasi-homogeneous catalysts, and cracking-initiating additives. Subsequently, the potential challenges of each approach in practical applications are analyzed. Furthermore, based on the current research findings, we outline future research directions with the expectation of facilitating the advancement of efficient cracking technologies for endothermic hydrocarbons.