The polymer chain distribution in solution-cast thin films of poly(2-methoxy-5-(2＇-ethylhexyloxy)-1,4-phenylene vinylene) (MEH-PPV) has been investigated by X-ray diffraction. The results show that regardless of the solvent, chain orientation in cast films is anisotropic; the PPV backbones and the planes defined by the benzene rings within the PPV backbones are predominantly parallel to the film plane. When drop-cast from tetrahydrofuran (THF), the preferred solvent for preparation of MEH-PPV films with low threshold in gain narrowing experiments, this anisotropy in chain orientation is more pronounced, and the crystallinity is higher.