A polymeric surfactant (PFSA) was synthesized by the aqueous free-radical copolymerization using acrylamide, sodium 2-acrylamido-2-methylpropane sulphonate, allyl-capped octylphenoxy poly(ethylene oxide) with the polymerization degree of 20 (AOP), and 1H, 1H, 2H, 2H-perfluoro-1-decyl p-vinylbenzyl ether (VF). PFSA exhibited both of the good surface and interfacial activities and the thickening behavior. It could be used in enhanced oil recovery to increase both sweep and oil-displacement efficiencies. The critical micelle concentration (CMC) of PFSA was 0.1 g/L in aqueous solution. The spherical micelles with the diameter of 100 nm were formed at CMC, and numerous compact worm-shaped micelles were observed above CMC. The interfacial tension was 0.027 mN/m for the 0.1 g/L PFSA solution containing 5 g/L NaCl and 0.209 g/L SDBS. The PFSA solutions still showed low interfacial tensions at high NaCl concentrations and temperatures, respectively, because of the incorporation of both VF and AOP containing long PEO.