In the search for new ways to combine the appealing simplicity of solution processing methods and the need for a high performance of the active layer of organic (opto)electronic devices, the possibilities given by the joint use of well‐established casting techniques and post‐treatment procedures are explored, as well as new and unconventional deposition protocols to tailor self‐assembled architectures with a high degree of order at different length scales, from the subnanometer up to the macroscopic scale. In fact, even the same organic molecule can give rise to different molecular architectures which, in turn, may offer the possibility to exploit a large variety of new functionalities of the deposited materials, paving the way towards the fabrication multifunctional organic‐based devices.