This section describes the preparation and characterization of investigated systems. The preparation part involves solely colloidal suspensions, mixture of nanoparticles and surfactants, micelle solutions, polyelectrolytes solutions, and the substrate cleaning process and modification. Zeta potential, contact angle, surface tension, surface topography and surface thickness are characterized via relevant techniques. The structuring of colloidal suspensions in confinement and in bulk are determined by colloidal-probe atomic force microscopy and small angle X-ray scattering, respectively. The detailed experimental procedures and data-analyzing methods are presented as well.