An improved Langmuir-Blodgett self-assembly process combined with Ag-assisted wet chemical etching for the preparation of ordered silicon nanowire arrays is presented in this paper. The new process is independent of the surface conditions (hydrophilic or hydrophobic) of the substrate, allowing for depositing a monolayer of closely packed polystyrene nanospheres onto any flat surface. A full control of the morphology of the silicon nanowire is achieved. Furthermore, it is observed that the formation of porous-Si at the tips of the nanowires is closely related to the release of Ag nanoparticles from the Ag mask during the etching, which subsequently redeposit on the surface initially free of Ag, and these Ag nanoparticles catalyze the etching of the tips and lead to the porous-Si formation. This finding will help to improve the resulting nano- & microstructures to get them free of pores, and renders it a promising technology for low-cost high throughput fabrication of specific optical devices, photonic crystals, sensors, MEMS and NEMS by substituting the costly BOSCH process. It is shown that ordered nanowire arrays free of porous structures can be produced if all sources of Ag nanoparticles are excluded, and structures with aspect ratio more than 100 can be produced.