Effect of titania nanoparticles modified with 3 wt% [3‐(methacrylloxy)propyl]trimethoxysilane (m‐TiO2 NPs) and zirconia nanoparticles modified with 3 wt% (3‐glycidyloxypropyl)triethoxysilane (m‐ZrO2 NPs) on properties and morphology of acrylic emulsion polymer coating was investigated. With suitable weight ratio of m‐TiO2/m‐ZrO2 NPs, the acrylic coating could be improved abrasion resistance, weather durability, reflectance index (400–1400 nm) as well as thermal‐oxidation stability in comparison with the coatings having the same content of single modified nanoparticles. The starting thermal degradation temperature of acrylic coating filled by mixture of m‐TiO2 NPs and m‐ZrO2 NPs was approximately 10°C higher than that of the acrylic coating contained separately modified nanoparticles. The mixture of m‐TiO2 NPs and m‐ZrO2 NPs were used in solar reflective paint. Replacement of rutile TiO2 microparticles by 1 wt% mixture of modified nanoparticles, the solar reflective paint (SRP) could be improved water resistance and cooling performance. The water permeability of the SRP coating with mixture of modified nanoparticles was reduced by nearly 50%. The results of cooling performance test indicated that SRP loaded 1 wt% (m‐TiO2 NPs and m‐ZrO2 NPs) (weight ratio of 1/1) replaced 1 wt% TiO2 microparticles could reduce outside temperature of chamber test by nearly 11°C and ambient inside temperature of chamber test by 7.5°C. This novel solar reflective paint is considered as promising material for outdoor applications.