Micro/nanostructures have broad applications in diverse application fields, such as surface enhanced Raman spectroscopy (SERS), photocatalysis, field emission, photonic crystals, microfluidic devices, electrochemical devices, etc. Using polystyrene (PS) spheres formed monolayer colloidal crystal templates as masks, scaffolds, or molds with different materials growth techniques, many different periodic nanostructured arrays can be obtained with the building units varied from nanoparticles, nanopores, nanorings, nanorods, to nanoshells. Significant progresses have been made on the synthesis of micro/nanostructures with efficient SERS response. In this review, we mainly focus on the various PS template-based fabrication techniques in realizing micro/nanostructured arrays and the SERS applications. Micro / nanostructures have broad applications in diverse application fields, such as surface enhanced Raman spectroscopy (SERS), photocatalysis, field emission, photonic crystals, microfluidic devices, electrochemical devices, etc. Using polystyrene (PS) spheres formed monolayer colloidal crystal templates as masks , scaffolds, or molds with different materials growth techniques, many different periodic nanostructured arrays can be obtained with the building units varied from nanoparticles, nanopores, nanorings, nanorods, to nanoshells. Significant progresses have been made on the synthesis of micro / nanostructures with efficient SERS response. In this review, we mainly focus on the various PS template-based fabrication techniques in realizing micro / nanostructured arrays and the SERS applications.