In this study, we present a novel electrochemical technique for the fabrication of macro-meso-microporous multilayer structures. Based on systematic investigation of HF/H2O2/ethanol electrolyte system, all three types of pores (smooth macropores, branched mesopores and spongy micropores) can be produced respectively on highly-doped n-type silicon substrate by varying the applied current density, which determines the pore sizes and morphologies. By applying a multi-step current modulation during anodization, a multilayer consisting of three different pore morphologies (macro-, mesa-, and micro-pores), as well as several types of multilayer structures with two different pore morphologies, was fabricated on the same silicon substrate using the same electrolyte. A wide range of porosities (30-82%) can be easily achieved with this approach. The current-burst-model is employed to interpret the mechanism concerning such three types of pores formation. (C) 2012 Elsevier Ltd. All rights reserved.