A detailed structural and orientational study on thin films of poly([n,n′-bis(2-octyldodecyl)-11naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5′-(2,2′-12 bithiophene)) (P(NDI2OD-T2)) with low molecular weight is reported. The combination of grazing incidence diffraction with varied depth sensitivity and powder diffraction using synchrotron radiation provide new insights on the unit cell, confirming polymorphic behavior, and configuration ratio, i.e. face- versus edge-on. The effect of thermal treatment on microstructure is also presented. Insights of the macromolecule configuration, specifically the reciprocal position of bis-dicarboximide and bi-thiophene residues, are derived from simulation of 2D images based on reliable models.