In this paper, a series of colloidal polymers with various Tg, composition, and sphere size were synthesized by surfactant-free emulsion polymerization and dispersion polymerization methods and then blended with colloidal silica particles to obtain polymer/silica nanocomposite latexes. When these nanocomposite latexes were forced dry at high temperature (e.g., 110℃) for 2h, a three-dimensional ordered porous structure was directly obtained. Neither complex processes nor removal of any templates like in a templating method is needed. These ordered pores should form from the top surface and then propagate layer by layer from the top surface to substrate.