In this paper, we describe a convenient approach for fabricating two-dimensional, ordered TiO2 bowl-like structure and inverted-bowl-like structure patterns consisting of submicrometer arrays on a self-assembled monolayer film, for the first time using a surface-modified polystyrene colloidal monolayer as the template. Typically, the well-ordered two-dimensional TiO2 bowl-like structures were obtained by liquid phase deposition within the interstitial voids in assemblies of polystyrene spheres followed by the dissolution of the polystyrene template with dichloromethane. Otherwise, through a simple wet treatment by immersing in the sulfuric acid at 50 degrees C, the surface characteristics of polystyrene were turned from hydrophobic to hydrophilic. The ordered inverted-bowl-like structures could be prepared on this treated surface. We believe that this method could be extendable to colloidal template with smaller dimensions, and to periodic arrays made of other materials.