Liquid fuel is flammable and hazardous, and a pool fire is one of the most serious disasters. Therefore, it is important to develop high-performance firefighting agents. To synthesize aqueous film-forming foam (AFFF) formulations, two C6 short-chain fluorocarbon surfactants Capstone 1157 (FC1157) and sodium perfluorohexylethyl sulfonate (SF852) with different hydrophilic groups were introduced, and three hydrocarbon surfactants sodium dodecyl sulfate (SDS), decyl glucoside (APG0810), and coco glucoside (APG0814) were chosen. The AFFF formulations based on the short-chain fluorocarbon-hydrocarbon compounding system were developed, and the firefighting performance of the formulations was assessed according to the standard pool fire extinction test. The results indicated that amphoteric FC1157 was slightly more effective than anionic SF852 in extinguishing small-scale pool fires and could reduce heat flux more effectively than SF852. Fluorocarbon surfactant FC1157 has been shown to suppress large pool fires much better than SF852, possibly due to its higher foam stability, higher foaming property, lower dynamic surface tension, and lower bubble coarsening rate. Both formulations we studied were more effective than commercial AFFF formulations. A concentration of 0.1-0.3% of FC1157 in an AFFF solution was optimal for extinguishing high-boiling-point oil fires.