The self-assembled long-range ordering, packing morphology and thermal behavior of a series of polyhedral oligomeric silsesquioxanes (POSS) T-8 cage systems with long n-alkyl chain pendant groups is presented. State-of-the-art time-resolved small- and wide-angle X-ray scattering (SAXS/WAXS), thermal and optical techniques were used to elucidate their morphology. X-ray scattering showed long-range crystalline ordering where the alkyl chains align in an axial disposition from the POSS core giving a "rod-like" self-assembled packing morphology with a length-scale correlating to the overall molecular dimensions. Phase transitions observed by thermal methods were comparable to those seen in the crystallization of bulk n-alkanes. Optical measurements and crystallization kinetics confirmed a lamellar macromorphology again being similar to the crystal structure of bulk n-alkanes. This study reveals for the first time, the direct effect that the alkyl chain length has on the self-assembled crystalline packing morphology of this novel and potentially commercially relevant, series of POSS systems.