Polymer-based colloid lithography represents the very effective approach for creation of a large-scale template for subsequent surface modification. Utilization of this approach, however, is significantly restricted by the ability of used micro/nanospheres to create only limited number of symmetrical structures. In this work, we propose the treatment of polystyrene (PS) microspheres in the solvent vapor, before subsequent surface grafting with diazonium salts as an alternative method for the creation of structures with required geometry and symmetry. Application of vapor treatment allows the effective modification of PS microspheres screened area and. As a result, the subsequent grafting procedure leads to the creation of ordered micropores array with tunable size and height. Combination of different solvents with slight heating was studied and found to be suitable for further creation of different surface grafting pattern. The success of surface grafting through the treated PS microsphere mask was verified using Raman spectroscopy and AFM microscopy techniques.