Two kinds of nanocrystalline Tin doped indium oxide (or indium tin oxide: denoted ITO hereafter) powders with different crystal structures – rhombohedral and cubic – were prepared using a coprecipitation method through the control of pH of a mixing solution and aging time after coprecipitation. The two powders have the same particle size of 15 nm in diameter but different morphologies (spherical for rhomboheral and rectangular for cubic). The gaseous ethanol sensing characteristics of the sensors prepared by the two ITO powders were quite different. The sensitivity of rhombohedral ITO sensor was high compared to that of the cubic ITO sensor across all temperatures. The reason for this is explained through the viewpoint of the binding energy of XPS and the surface structure relating to the crystal structure.