From simple pocket calculators to mobile telephones and liquid crystal display (LCD)-TV, over the past few decades, devices based on LCD technology have proliferated and can now be found in all conceivable aspects of everyday life. Although used in cutting-edge technology, it is surprising that a vital part in the construction of such displays, namely the alignment layer, relies essentially on a mechanical rubbing process, invented almost 100 years ago. In this paper efforts to develop alignment layers (also called command layers) by processes other than rubbing, namely self-assembly of molecular and macromolecular components will be discussed. Two topics will be presented: (i) tuneable command layers formed by stepwise assembling of siloxane oligomers and phthalocyanine dyes on indium tin oxide surfaces and (ii) command layers formed by self-assembly of porphyrin trimers. The potential use of these layers in sensor devices will also be mentioned.