Intumescent fireproof coating (IFC) can effectively slow down the temperature rise of base materials by constructing intumescent heat isolation chars. Expandable graphite (EG), combined with a typical intumescent flame-retardant system, shows an excellent expansion effect. However, it is difficult to be evenly dispersed in the coating system due to its low surface energy, thus limiting its application in IFC. In this research, EG encapsulated by polyvinyl alcohol (PVA) film was used in combination with conventional intumescent flame retardants to prepare a fireproof coating. Due to the increased hydrophilicity caused by the hydroxy groups of the PVA, both the dispersion and adhesion of EG can be greatly improved in the coating. Additionally, PVA also plays the role of a charring agent to further upgrade the quality of the produced carbon layer. The prepared IFC displays a satisfying synergistic effect. The experimental results showed that the back-surface temperature of the steel plate coated by PVA@EG was reduced to 232 °C after 20 min, far lower than the 250 °C of the unmodified EG system, and the thermal insulation performance was enhanced significantly. Compared with the untreated EG coating, the HRR, THR, and TSR decreased by 79.5 %, 86.0 % and 24.8 %, respectively, and combustion and smoke suppression performance were improved greatly. All in all, PVA@EG endows the coating with superior flame-retardant and thermal insulation performance and greatly improves the safety of steel structures in buildings.