An electroless chemical etching technique using polystyrene nanospheres as self-assembled mask is developed to fabricate size-controllable, periodic silicon nanopillars (NPs) and subsequent nanocones (NCs) arrays. The Si NCs are obtained based on the NPs structure using cost-effective ammonia-related etching chemistry. The diameter, height, and periodicity of the NCs can be systematically controlled. This method is potentially beneficial to many device applications including super-capacitors, batteries, solar cell, etc.