Waterborne fluorocarbon coatings are gaining popularity as a more environmentally friendly replacement for traditional solvent-based coatings because of its corrosion resistance and antibiofouling properties. However, the environmental unfriendliness of small molecular emulsifiers used, the occurrence of flash rusting, and the inability to self-repair after accidental damage restrict its application in the marine industry. Here, a redox-responsive copolymer (PMx) was synthesized by the amphiphilic nature of waterborne polyurethane as microreactors, which was employed as coatings (PMx/WPU) with anti-flashing rust, antibiofouling, and self-repairing functions. The copolymer was polymerized from chlorotrifluoroethylene (CTFE), vinyl acetate (VA), and a special monomer conjugated to the corrosion inhibitor 2-benzothiazolethiol (MBT) through disulfide bonds, in which MBT can be released through disulfide bond breaking in a reducing environment, effectively preventing the occurrence of flash rusting. The combination of the repelling properties of the fluorinated groups and the bactericidal action of the MBT results in PMx/WPU coatings with excellent antibiofouling properties. Additionally, the reversible hydrogen bonds in the polyurethane provide the PMx/WPU coatings with excellent self-repairing ability (93.9%). Our study presents a new approach to polymerize fluoro-substituted ethylene monomers using polyurethane as microreactors, enabling the preparation of waterborne fluorocarbon coatings with anti-flashing rust, antibiofouling, and self-repairing properties for practical applications.