In this study, the composite coating materials with improved thermal insulation property were prepared by incorporating the hollow micro-spheres with high heat transfer resistance. The UV curable resin system consisting of hexa aliphatic urethane acrylate (UP118), trimethylolpropane triacrylate (TMPTA), 1,6-hexanediol diacrylate (HDDA), and photoinitiator (Irgacure184) was employed as an organic binder. The glass substrates were coated by the prepared composites via bar coating method and cured under UV radiation. The optical transparency, thermal insulation property, adhesion, and surface hardness of the glass coated with composites containing different type of micro-spheres were investigated. The incorporation of micro-spheres with only 20 vol% of content resulted in remarkable improvement in the thermal insulation property of the coated glass. In addition, the transparent coated glass with light transmittance of about 80% could be obtained when silica micro-sphere (SP) was used as a thermal barrier.