Multifunctional road marking coatings with the functions of high-temperature stability, degradation of exhaust gas, and self-cleaning are of great significance for the safe operation and environmental protection of tunnels. This article uses active acrylic resin and an organosilicon hydrophobic agent as the base material, selects expanded vermiculite and glass microspheres as insulation fillers, and uses ammonium polyphosphate, pentaerythritol, melamine, and aluminum hydroxide as high-thermal-stability systems to prepare a two-component road marking coating base material. Then, nano SiO2 and modified nano TiO2 are added as modifiers to prepare a multifunctional road marking coating for tunnels. The physical and chemical properties of multifunctional road marking coatings are evaluating based on laboratory tests including thermogravimetry and derivative thermogravimetry, differential scanning calorimetry, infrared spectroscopy, scanning electron microscopy, exhaust degradation, and contact angle tests. The results indicate that the developed multifunctional road marking coating effectively reduces the thermal conductivity of the carbon layer through physical changes in the flame retardant system and the heat resistance formed by the high breaking bond energy of nano SiO2 during the combustion process. It forms a ceramic-like structure of titanium pyrophosphate with nano TiO2 that is beneficial for improving flame retardancy without generating harmful volatile gases and has good flame retardant properties. N–V co-doping reduces the bandgap of TiO2, broadens the absorption range of visible light by nano TiO2, improves the catalytic efficiency of visible light, and achieves the degradation efficiency of the four harmful components NOx, HC, CO, and CO2 in automotive exhaust by 23.4%, 8.3%, 2.5%, and 2.9%, respectively. The solid–liquid phase separation in the multifunctional road marking coating in the tunnel causes the formation and accumulation of nano SiO2 and TiO2 particles on the coating surface, resulting in a microstructure similar to the “micro–nano micro-convex” on the lotus leaf surface and making a water droplet contact angle of 134.2° on the coating surface.