We investigated chemical composition, crystal structure and electrical and optical properties of rf-sputtered thin films deposited from Zn3In2O6 polycrystalline target at different substrate temperatures. Continuous structural variation from Zn(3)Tn(2)O(6) to In2O3 through Zn2In2O5 was observed on the deposited films with increasing the substrate temperature. ICP analysis of the films showed the ratio of zinc to indium decreased with increasing the temperature, in a good accordance with the structural variation. Conductivity of the film gradually increased in the temperature range where Zn3In2O6 changed to Zn2In2O5 but abruptly decreased in the range where In2O3 phase appeared. Optical band gap increased when the film was mainly composed of In2O3.