We report polarized optical transmission and reflection measurements which are used to determine the orientation of polymer chains in spin‐cast thin films of soluble, electroluminescent polymers. We find that the polymer chains lie primarily in the plane of the film. This result has three important implications for polymer light emitting diodes: the electroluminescence is preferentially emitted propagating perpendicular to the polymer film; the relevant dielectric and electrical transport properties are those perpendicular to the polymer chains; and large area, uniform devices can be produced by spin casting.