Carefully designed ZnO nanowire-film hybrid nanostructure, composed of a bottom ZnO film, ZnO nanowire arrays, and a top ZnO film, was consecutively fabricated by adjusting the supersaturation conditions using a metal-organic chemical vapor deposition (MOCVD) to utilize the vertically aligned ZnO nanowires as the oxygen sensors. The decrease of current flow through ZnO nanowire arrays increasing oxygen pressure showed the high potential for the application of the ZnO hybrid nanostructure to the oxygen sensors. In addition, it was confirmed that the oxygen sensing characteristics of this hybrid nanostructure were attributed to the defects near the surface of the nanowires.