We have developed a general two-step synthesis of large-scale arrays of one-dimensional (1D) nanostructured Co3O4 directly on various substrates. Throughout a controllable hydrothermal process using urea as mineralizer and hereafter with a postcalcination process under air atmosphere, Co3O4 1D nanostructure arrays have been grown firmly on insulating substrates, such as glass slides and ceramics, which is quite convenient for the construction of gas sensor devices without any extra electrode preparation process. Furthermore, this direct-growth approach can be readily extended to conductive substrates (ITO, Ti, Fe−Co−Ni alloy), and meanwhile due to the robust mechanical adhesion and one-dimensional carrier transportation architecture firmly contacted to the metal, the metal substrate-supported Co3O4 arrays could act as a promising electrode material and be straightforwardly integrated into electronic and electrochemical nanodevices.