The crystalline orientation of oligothiophenes has a profound effect on the electronic properties of the materials, which are of interest for example in the construction of all‐organic field‐effect transistors. Here, an X‐ray diffraction study of oligothiophene films is reported and the possible routes to improving the crystalline orientation discussed. It is found that α‐substitution or indeed heating of the substrate can lead to increased orientation of the oligomers.