Spatially organized macroporous thin films made of close-packed nanocrystals (see Figure) can be formed using a single-step dispersion evaporation technique. Water condensation is induced, in which droplet coalescence is prevented by interfacially active nanocrystals, allowing close-packed arrays of monodisperse water droplets to form. The hydrophobic nanocrystals then mold themselves around the water droplet template, leading to highly ordered porous nanocrystal films.