Highly ordered organic films must be prepared and characterized if the electrical properties of future organic-based electronic devices are to be improved, because it is only then that our understanding of intermolecular transport in polymer films can increase. An atomic force microscopy study is presented that shows that quinquethiophene can be physisorbed on SiO2 to form highly ordered layers. A change from layer-by-layer to multilayer growth is reported to occur upon completion of the second monolayer.