Low-temperature casting of high molecular weight (HMW > 40 kDa) regioregular poly(3-hexylthiophene) (P3HT) is demonstrated to yield highly crystalline P3HT thin films with well defined and preferentially edge-on oriented [(100) contact plane] nanocrystallites on the pure and silanized Si/SiO2 substrates. Transmission electron microscopy and X-ray diffraction provide evidence for the increase in preferential edge-on orientation of P3HT-conjugated backbone while decreasing the film preparation temperature below room temperature. The optimum growth temperature is about -12 degrees C for the given concentration (2 mg/mL in CHCl3). The reduced evaporation rate of the solvent results in a better selection of the thermodynamically stable orientation of nanocrystallites onto the substrate. The degree of preferential orientation and size of the crystallites can be further increased on n-octadecyltrichlorosilane-treated SiO2 substrates as well as by annealing the films at 200 degrees C for 1 h. (c) 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012