In this paper, the fabrication of two-dimensional photonic crystals using microspheres of polystyrene is investigated. The wedge shaped method is used to grow a hexagonal self-assembled monolayer structure with polymeric microparticles on a glass substrate. In this work the effect of the cell’s internal angle on the monolayer’s density and quality is studied. The proposed two-dimensional photonic crystals can be used as a template for fabrication of various two-dimensional nanostructure arrays and also other kinds of photonic crystals.