In this study, a composite material consisting of perfluorinated quaternary silane-modified graphene oxide and modified CeO2 nanoparticles was prepared, and a hydrophobic, corrosion-resistant, self-cleaning and anti-icing composite coating was prepared by combining the composite material with polyphenylene sulfide (PPS) through high-temperature curing in a simple spraying method for the protection of iron sheets. The results show that the composite coating has excellent corrosion resistance, strong mechanical properties and certain photothermal properties. When the content of perfluorinated quaternary silane modified CeO2 nanoparticles with graphene oxide (P-GKC) was 10 wt%, the composite coating had a water contact angle of 145.6 ± 3° and a sliding angle of 5 ± 1°, with good hydrophobicity and low surface energy. Meanwhile, the hydrophobic modification of perfluoroquaternary silanes reduced the surface energy of the particles in the composite coatings and greatly improved the hydrophobicity. Surface temperature and laser irradiation tests of the composite coatings showed that the photothermal properties of the composite coatings were better than those of the single PPS and graphene oxide (GO) coatings, with good photothermal cycling stability.The Tafel curves and the EIS results showed that the PPS/10 wt% P-GKC composite coatings had the best corrosion resistance, with a corrosion current density of 5.01 × 10−9A cm−2. After 200 h of salt spray test in 3.5 % NaCl environment, the PPS/10 wt% P-GKC composite coating still has good substrate protection effect, which provides a practical basis for the research of composite coating anticorrosion.