The effect of chemical pretreatments on the electrochemical etching behavior of aluminum was investigated with the topographic studies of surface and the analysis of initial potential transients. Two-step pretreatments with H3PO4 and H2SiF6 result in a high density of pre-etch pits on aluminum surface by the incorporation of phosphate ion inside the oxide film and the removal of surface layer by aggressive fluorosilicic acid solution. It generates a high density of etch pits during electrochemical etching and results in the capacitance increase of etched Al electrode by expanding the surface area, up to 61.3 μF/cm2 with the pretreatment solution of 0.5M H3PO4 at 65°C and 10 mM H2SiF6 at 45°C.