High density ordered Si nanowire arrays can be fabricated from a Fe2O3 template annealed from polystyrene (PS) microsphere layers via a metal-assisted chemical etching method. The metal mesh films, containing position-and density-defined pores that determine the position and density of the remaining structures after etching, are extremely important for achieving high quality Si nanowires. By adding a structural inversion process, a Au metal mesh with arrays of high density nanopores is devised as a catalyst for metal-assisted chemical etching of silicon. The density of Si nanowires can be increased to two times that of the single-layer PS microspheres and further to three times when a double layer of PS microspheres is introduced. The two-step template method for the preparation of high-density Si nanowires shows great potential in the fields of nanofabrication and nanoelectronics.