This study investigates the nature of interactions between the molecules of polyhedral oligomeric silsesquioxane (POSS) containing silanol functionalities (silanol–POSS) and di(benzylidene)sorbitol (DBS) encountered in the development of nanocomposite fibers from the compounds of POSS, DBS, and isotactic polypropylene (iPP). The interactions were investigated using Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), nuclear magnetic resonance (NMR) spectroscopy, mass spectrometry, and oscillatory shear rheology. Mass and NMR spectrometry revealed that the molecules of silanol–POSS and DBS formed several amorphous noncovalent molecular complexes promoted by hydrogen bonding. More abundant complex formation was observed with silanol–POSS molecules carrying four silanol groups and phenyl substitutions. Such complex formation deterred fibrillation of DBS when the compounds of iPP, DBS, and silanol–POSS were cooled from homogeneous melt states. It was also revealed that POSS–DBS complexes were of much lower viscosity than iPP.