By using the self-assembling process, it is possible to generate a large number of various structural organizations in which individual elements get together into regular patterns under suitable conditions. Two-dimensional self-assembled networks placed on solid and flexible substrates were obtained from solutions containing nano- and micro sized polymer spheres by evaporating the solvent in proper environmental conditions. The entire procedure is uncomplicated and it has been demonstrated as readily reproducible. The parameters used for the duration of the process are as well very easy to control.