Currently, most thin-layer expandable coatings are polymer-based, with very few inorganic expandable coatings. Due to the high environmental friendliness of inorganic coatings, studying new types of inorganic coatings is of great significance. A novel amorphous aluminum phosphate-based flame-retardant coating was prepared by modifying it with nano-silica, hollow silica beads, hollow glass microspheres, and boron carbide. A comprehensive study was conducted on the flame retardancy and thermal insulation performance, composition and structural evolution under flame and physical and chemical properties, and the mechanisms of flame retardancy and thermal insulation were elucidated. Large-plate combustion testing, bonding strength testing, XRD, IR, TG-DSC, and SEM testing were all applied in this work. The synergistic effect of the four fillers was very obvious, and a series of AP22XY (nano-silica/silica beads/hollow glass microspheres/boron carbide = 2:2:0:4, 2:2:1:3, 2:2:2:2, 2:2:3:1, 2:2:4:0) coatings were prepared. The change in the ratio of glass microspheres to boron carbide had a significant impact on the composition and structural evolution of the coating, thus reflecting its effectiveness as a flame retardant and thermal insulation. Although decreasing the ratio would promote the formation of borosilicate glass and Al18B4O33and improve the thermal stability of coatings, the structure inside of the coating, especially the skeleton, would be dense, which is not conducive to thermal insulation. When the ratio of glass microspheres to boron carbide is 3:1, AP2231 shows the best fire resistance. Under the combustion of butane flame at about 1200–1300 °C, the backside temperature reaches a maximum of 226 °C at 10 min, and then the temperature gradually decreases to 175 °C at 60 min. This excellent performance is mainly attributed to three aspects: (1) the foaming and expandability of coatings when exposed to fire, (2) the multiple endothermic reactions the coating undergoes, and (3) the improvement effect of boron carbide. Additionally, AP2231 shows the best bonding performance with a strength of close to 4.5 MPa after combustion, because of the appropriate content matching between borosilicate glass, Al18B4O33, and hollow glass microspheres. The coating has potential application prospects in the construction and transportation fields, such as the protection of structural steel, fire prevention in subways and tunnels, and the prevention of lithium battery fires.