The work aims to improve insulation performance of building energy-saving coatings and providing certain reference significance for building energy saving coatings featuring in multiple thermal insulation mechanisms. Undersurface/surface composite building energy-saving coatings were prepared with hollow glass micro-bead as undersurface coatings, coatings containing nickel titanium yellow as surface coatings and self-made composite emulsion as adhesive. What’s more, effects of content of nickel titanium yellow on properties of coatings were investigated. Properties of nickel titanium yellow and coatings were characterized using XRD, ultraviolet/visible/near-infrared spectrophotometer, infrared emissivity measurement device, precise colorimeter and scanning electron microscope. Infrared lamp was used to simulate sunlight heat source and analyze insulation performance of the coatings. Rutile nickel titanium yellow was a rutile-type structure exhibiting excellent reflective characteristic in visible light and near-infrared light, its average reflectance in visible light and near-infrared band was 72.61%. The average reflectance of coatings in visible light and near-infrared band was influenced by content of nickel titanium yellow to a certain extent. Provided that nickel titanium yellow was 20%, near infrared average reflectance of the composite coatings could be up to 66.75%. Meanwhile, long wave emissivity of coatings in wave band of 3~5 μm and 8~14 μm was 0.95 and 0.94, respectively. Equilibrium temperature on reverse side of the composite coatings was 2.4% lower than that of surface coatings with the same content of nickel titanium yellow. Thus, insulation performance of building energy-saving coatings can be improved by using barrier-reflection type/subface-surface composite structure, optimum content of the pigment shall be 20% in practical application.