Submicron-sized polymeric colloidal particles can self assemble into 3-dimensional (3D) opal structure which is a useful template for photonic crystal. Narrowly dispersed polymer microspheres can be synthesized by emulsion polymerization in water using water-soluble radical initiator. In this report, we demonstrate a facile and reproducible emulsion polymerization method to prepare various polymeric microspheres within 200 - 400 nm size ranges which can be utilized as colloidal photonic crystal template. By controlling the amount of monomer and surfactant, monodisperse polymer colloids of polystyrene (PS) and acrylates with various sizes were successfully prepared without complicated synthetic procedures. Such polymer colloids self-assembled into 3D opal structure exhibiting bright colors by reflection of visible light. The colloidal particles and the resulting opal structures were rigorously characterized, and the wavelength of the structural color from the colloidal crystal was confirmed to have quantitative relationship with the size of constituting colloidal particles as predicted by Bragg equation. The tunability of the structural color was achieved not only by varying the particle size but also by infiltration of the colloidal crystal with liquids having different refractive indices.