In this paper, mesoporous antimony doped tin oxide (ATO) microspheres are synthesized via a solvothermal method from a methanol system with the surfactant followed by a thermal treatment process. Morphology studies reveal that the spherical products obtained by polyvinylpyrrolidone (PVP) templating result in a higher uniformity in size. Such obtained ATO microspheres with a secondary particle size ranging between 200 and 800 nm consist of packed tiny nanocrystals and have high specific surface area (∼98 m2 g–1). The effect of Sb doping on the structural and electrical properties of SnO2 microspheres is studied. Because of the substitution of Sn4+ with Sb5+ accompanied by forming a shallow donor level close to the conduction band of SnO2, a lower resistivity of powder pellet can be achieved, which corresponds to the spectrally selective property of films. The application of ATO microspheres provides an example of transparent coatings; depending on Sb concentration in SnO2 and solid content of coatings, transparent films with tunable solar-heat shielding property are obtained.