Due to regulatory restrictions on long?chain fluorocarbon surfactants, the synergistic mechanisms of short?chain composite systems developed as alternatives remain unclear, hindering the advancement of high?performance and environmentally friendly firefighting agents. This review systematically outlines optimization strategies for short?chain fluorocarbon firefighting agents, including molecular engineering approaches (chain?length control, zwitterionic design) and compounding techniques (fluorocarbon/hydrocarbon synergy). By synthesizing existing research, it highlights that C₄—C₆ short?chain surfactants strike a balance between surface activity and environmental friendliness and composite systems significantly reduce critical micelle concentration and fluorine consumption, simultaneously enhancing foam stability. The review summarizes synergistic mechanisms in compounding including electrostatic interactions between anions and cations promoting dense film formation, and conformational matching inhibiting aqueous migration. It also establishes quantitative relationships spanning from microscopic molecular arrangements to macroscopic properties, such as interfacial tension and foam stability. This study provides theoretical reference for understanding the mechanism of compounding and promoting the rational design of fire extinguishing agents.