Masking with polystyrene (PS) nanospheres, also known as colloidal lithography, is suitable for many technological applications. In this study, an evaporation-driven self-assembly process was applied and the surface coverage behavior of the nanospheres was monitored in terms of the surface coverage rate of the PS nanospheres and the change in the amount of hexagonal closed packed structures as a function of the suspension ratio, the drying temperature, and the tilt angle. Using this method, a well-ordered and homogeneous PS monolayer with a surface coverage rate of 82% (or relative surface coverage rate of 98%) was achieved on a 1×1 cm2 substrate surface.