Supramolecular complexes of C-60 and C-70 encapsulated within the cavity created by the helical superstructure of syndiotactic poly(methyl methacrylate) (s-PMMA) were aligned by elevated-temperature electrospinning. Using C-13 solid-state NMR, encapsulation of C-60 within the nanotubular cavity was confirmed by downfield chemical shifts and significantly shorter spin spin relaxation times compared to C-60 physically mixed with s-PMMA. Thermal analysis revealed a melting endotherm at 180 degrees C for the C-60/s-PMMA electrospun fibers that is consistent with formation of the nanotubular supramolecular complex. Based on the syndiotactic content of the s-PMMA and,the gravimetrically determined fullerene content in the electrospun fibers, 82% of the nanocavity is filled with C-60, dropping to 55% filling with C-70. The fibers were macroscopically aligned by electrospinning onto a split collector plate for analysis of molecular alignment. Wide-angle X-ray scattering azimuthal scans revealed high degrees of molecular-level alignment, with an order parameter of 0.70 for the C-60/s-PMMA nanopods. (C) 2014 Elsevier Ltd. All rights reserved.