Foam extinguishing agents can effectively control or extinguish fires by blocking oxygen, lowering fuel temperature and preventing fuel vapor release from contact with air, and its key component is surfactants that reduce the interfacial tension between water and oil. However, PFOS is strictly regulated due to its environmental and health hazards, so research to develop alternatives to PFOS is urgent. In this paper, the hazards of PFOS in fluorine-containing foam fire extinguishing agents are briefly described, and the structural characteristics and development status of three types of surfactants in foam fire extinguishing agents are discussed: 1) C4 short-chain perfluoroalkyl sulfonic acid surfactants; 2) fluorosurfactants containing branched chains of CF3CF2CF2C(CF3)2 groups and fluorocarbon surfactants with ether bonds introduced; 3) Silicone surfactants. Finally, the application prospects of three types of surfactants are prospected. This paper focuses on the analysis and summary of the current design strategies of substitutes from a structural perspective, which will provide guidance and support for the research and development of green and environmentally friendly foam fire extinguishing agents.