The effect of confinement on the crystallinity and chain orientation of ultrathin poly(di-n-hexylsilane) films has been investigated using UV absorption, fluorescence and IR spectroscopies. UV absorption measurements in a series of poly(di-n-hexylsilane) films having thicknesses between 50 and 3500 Angstrom have shown that, for thicknesses less than 500 Angstrom, the polymer backbone disorders and extensive crystallization of the films is hindered irrespective of molecular weight or surface hydrophobicity. Fluorescence studies showed that rapid energy transfer occurs from the disordered chain segments to the crystalline ones. The orientation of both the polymer backbone and side chains was probed with IR absorption and grazing incidence reflection measurements. The side chains are extended, although not completely in the all-trans conformation, with their carbon plane mostly perpendicular to the substrate. The backbone lies extended, with the polymer axis parallel to the plane of the film. The hexyl side-chains disorder in films less than 2000 Angstrom thick and this disordering occurs through the introduction of gauche bonds. Our findings suggest the possibility of using thickness to control the chain organization and morphology of a polymer thin film.