The work aims to improve thermal insulation and durability of coating by investigating optimal coating structure of building energy-saving coating. With a coating containing hollow glass micro-bead and titanium dioxide as base coat, and silica sol-styrene-acrylic composite emulsion as finishing coat, effects of different base coats and finishing coats on properties of building energy-saving coatings were investigated. Optimal combination scheme of base coat and finishing coat were obtained in method of orthogonal experiment. Comprehensive performance test was performed to the optimal combining scheme coating. What’s more, relevant mechanism was disscussed. Provided that color appearance of the coatings remained the same, the base coat could improve solar reflectance of the coating while the finishing coat could increase static contact angle, water resistance, stain resistance and ageing resistance of the coating, and reduced change rate of solar reflectance and chromatic aberration of the coating after pollution and artificial ageing treatment. Optimal combination scheme of coating was, hollow glass micro-bead and titanium dioxide in base coat as 5%, and mass ratio between styrene-acrylic emulsion/silica sol as 14∶1 in finishing coat. The solar reflectance and insulation temperature difference was 0.6455 and 6.9 ℃, respectively. The coating was of good overall performance and certain application value. Coating structure has certain effects on thermal insulation and durability of building energy-saving coating. Satisfactory performance can be obtained by changing coating structure during practical application.