Ordering of alpha,omega-dihexyl-alpha-quaterthiophene (DHalpha4T) thin films on substrates including friction-transferred polytetrafluoroethylene (PTFE) is explored. DHalpha4T exhibits a high-temperature mesophase from 81 to 181 degreesC. Textural analysis reveals this phase to be a tilted, highly ordered smectic phase. Upon cooling from the isotropic melt, the smectic phase grows layer by layer on many surfaces. Smectic thin films grown on friction-transferred PTFE exhibit a high degree of alignment with edge dislocations being the primary defect. Upon crystallization from the mesophase, the material retains for the most part the order of the mesophase. Growth of the smectic phase on directional surfaces such as friction-transferred PTFE appears to be a route to control of surface ordering of DHalpha4T.