Aqueous film-forming foam (AFFF) is a targeted product for liquid fuel fires and has the benefits of a long storage period and high fire extinguishing efficiency. However, because of the toxicity and bioaccumulation of the core raw material's long-chain fluorocarbon surfactant, traditional AFFF is being phased out. For this reason, three efficient AFFFs (F-1, F-2, and F-3; more details in Table 2) were designed using anionic surfactants (PBAF) with branched C6 perfluorinated chains, hexadecyltrimethylammonium bromide (CTAB), and dodecyl dimethyl betaine (BS-12) as core materials. Through comparison, F-1 shows excellent foaming ability (initial foam height is 86 mm) and foam stability (25% drainage time is 234 s). Moreover, F-1 exhibited excellent fire extinguishing and fire resistance performance: the fire extinguishing time was 33 s, and the fire resistance time was 831 s. This means that F-1 has enormous firefighting potential and can serve as a potential alternative to traditional AFFF.