Nanometer titanium dioxide was deposited on hollow fly ash beads using a chemical liquid deposition method. Surface modification of hollow fly ash beads with Ca(OH)(2) saturated solution resulted in the presence of calcium silicate hydrate. The surface modification had a great influence on the growth and micro-morphology of TiO2 nanoparticles on the surfaces of hollow beads. Electrostatic repulsive forces between the modified hollow bead surfaces and hydrated TiO2 were significantly reduced after the surface modification, favoring the formation of a homogeneous and uniform TiO2 film with high TiO2 loading. A possible growth mechanism of TiO2 coatings was proposed. Moreover, the near-infrared solar reflectance of hollow bead/TiO2 composite pigment reached 0.68, which was approximately 1.8 times as high as that of hollow beads. An approximately 28.1 degrees C decrease in temperature was obtained for the inner surface of a calcium silicate board coated with composite pigments. Therefore, hollow fly ash bead/TiO2 composite pigments are excellent candidates for near-infrared reflective pigments used in solar reflective coatings. (C) 2016 Elsevier B.V. All rights reserved.