The effect of molecular weight on the molecular aggregation structure of polymers bearing a pendant perylenediimide (PDI) side chain, designated PAc12PDI, was investigated using synchrotron radiation X-ray diffraction measurements. It was found that depending on molecular weight, either the main chain axis or the side chain axis behaves as the longitudinal axis in fiber samples and was aligned parallel to the fiber axis. A similar phenomenon is present in thin film samples, but was complicated by the additional influence of the interfacial free energy of the side chain group. Even in the case of the polymer with lower molecular weight, the face plane of PDI was found to show both parallel and perpendicular orientations to the substrate (i.e., flat-on and edge-on orientations). On the other hand, if the length of the main chain is sufficiently long with respect to the length of the side chain, the face plane of PDI was oriented perpendicular to the substrate, leading to an edge-on orientation in the thin film. (C) 2016 Wiley Periodicals, Inc.