A chemical strategy has been purposely designed to hierarchically assemble nanoscale building blocks at the interface of solution/solid. Typically, a solution containing precursor of one component and a metal foil as metal source of another component were employed, on the basis of proposed chemical reactions on expected interfaces. Proper reaction parameters including temperature, pH value etc. were selected to adapt both chemical reactions in solution and on the metal surface. Consequently, at the interface of solution and metal foil, two kinds of nanoscale building blocks deposited simultaneously leading to the current hierarchical assembly. This strategy has been applied to the fabrication of a series of functional materials, including Nb(2)O(5)/TiO(2), Nb(2)O(5)/LiF and ZnO/Co(3)O(4). The current strategy provides a convenient one-step route to achieve complex functional structures, which may have potential applications in a variety of fields such as solar cells, Li-ion batteries, electrochemical supercapacitors, catalysts as well as chemical, gas, and bio-sensors. (C) 2009 Elsevier Ltd. All rights reserved.