This study investigated the factors responsible for molecular interactions leading to self-assembly between the molecules of sorbitol and polyhedral oligomeric silsesquioxane (POSS) carrying organic and inorganic side groups. The study also assessed the utility of such molecular adducts as processing aids which will aid preparation of polymer compounds, films, and spun fibers. Several POSS molecules containing silanol functionalities and alkyl and phenyl substituents were used to separately evaluate the effects of hydrogen bonding and pi-pi interactions on formation of molecular adducts. The molecular adducts were studied using differential scanning calorimetry, wide angle X-ray diffraction, scanning electron microscopy, mass spectrometry, oscillatory shear rheology, and molecular dynamics simulation. The study revealed that POSS-sorbitol self-assembled structures were formed only when hydrogen bonding and it pi-pi interactions worked cooperatively. In addition, self-assembled molecules were of amorphous nature although POSS and sorbitol were crystalline. (C) 2012 Elsevier Ltd. All rights reserved.