Hexafluoroisopropanol functionalized polythiophene is able to build up an isotropic self-supporting network structure. The gel network can be melted and then transformed via mechanical shearing to form an anisotropic gel with the chains highly aligned along the shearing direction and the Conjugated backbones pi-stacked with respect to each other neighbors. The mechanism by which a dipole functionalized polythiophene can form a reversible network able to be deformed into structurally oriented films may be of interest in the development of novel processing routes for conjugated polymers.