An atmospheric process based on compressed CO2 is used to create stable clusters of small organic molecules. These clusters, 1–10 nm in size, are used as building blocks to assemble thin films on various substrates. Cluster assembly of these films is verified by using low-angle X-ray diffraction. The surface quality of these cluster-assembled films is similar to that of films usually prepared via the vacuum process. Several functional organic light-emitting diode devices have been prepared, in which only the doped emissive layer has been deposited by our process. The radiometric features and efficiencies of these devices match those of vacuum-built devices. Atomic force microscopy of these molecular clusters reveals that they are liquid-like at standard atmospheric conditions. Coatings of these clusters on cloth and stainless steel have been found to be superhydrophobic in nature.