The structure of thin films of poly(di-n-propylsiloxane), PDPS, was studied with a combination of optical and atomic force microscopy, electron diffraction, and grazing incidence X-ray diffraction. Two different morphological features are observed in the mesomorphic films. The lamellar ribbons are composed of the chains oriented parallel to the plane of the substrate in which the reciprocal space 10 vector is vertical. The other feature with a circular symmetry, the cylindrite, contains the chains parallel to the substrate normal. The cylindrites and needles are essentially the same mesomorphic lamellae that develop differently under the conditions of confinement. The crystallization of PDPS films does not change the gross morphological features developed during the mesophase formation and mainly proceeds via epitaxial growth of the a-crystal on the parent mesophase. Spontaneous alignment of the mesomorphic PDPS films on the PTFE-rubbed substrates allows fabricating highly crystalline inorganic polymer surfaces oriented on the scale of centimeters.