The structural investigation of poly(9,9-bis(2- ethylhexyl)fluorene-2,7-diyl) (PF2/6) in aligned thin films is presented. Formation of a thickness dependent triaxial texturing is identified in thermotropically aligned films. X- ray reflectivity measurements reveal good macroscopic quality, and polarized photoluminescence and dichroic ratios in absorption indicate clear axial alignment. Grazing-incidence X- ray diffraction shows axially aligned mesomorphic structure with a distinct arrangement of helices and large correlation lengths, indicating a high local lateral order. Theoretical models produced using molecular mechanics methods suggest 5/2- helicity. The polymer chains are parallel to the substrate in the c direction. In particular, the hexagonal-like cells are flattened in the direction of the surface normal and reveal two kinds of coexistent crystallites, a multiple orientation where the greater proportion of the crystallites have one crystal axis a perpendicular to the substrate surface, whereas a smaller proportion is aligned with the crystal axis a parallel to the surface. In thinner films the former class of orientation is usually dominant, while the proportion of the parallel orientation type increases with prolonged annealing.