The silicon (Si) microwires were fabricated by microsphere lithography using polystyrene (PS) beads monolayer. The Si wafer tailored into 40 x 40 mm2 was used as a substrate. The monolayer of 2.0 μm-sized PS beads was formed on substrates through convective assembly method. PS beads on substrates were tailored into smaller sizes by O2 plasma treatment using reactive ion etching (RIE). This controllable re-sizing process gave an opportunity to prepare the wire-array with various radii of Si microwires fabricated by using inductively coupled plasma (ICP)-etching. The convective assembly process was monitored in real-time through an optical microscope with a CCD camera. PS beads and structures of Si microwires were characterized using a scanning electron microscope (SEM) and the optical property was measured by the UV-Vis spectroscopy.