Self-assembled blends of PS-b-P4VP(PDP) supramolecules, obtained by hydrogen bonding of pentadecylphenol (PDP) side chains to poly(4-vinylpyridine), and poly(2,6-dimethyl-1,4-diphenyl oxide) (PPE) were investigated by thermal analysis and small-angle X-ray scattering (SAXS) and compared with blends of PS-b-P4VP and PPE. Differential scanning calorimetry (DSC) measurements showed a single composition dependent Tg of the PPE/PS layers for both systems, demonstrating that PPE is distributed throughout the PS layers. Furthermore, DSC showed that for the PPE/PS-b-P4VP(PDP) blends the presence of PDP is not restricted to the P4VP layers. Its partial presence in the PS-containing domains was confirmed by nuclear magnetic resonance (NMR) spectroscopy on PS−P4VP core−corona nanorods prepared from hexagonally self-assembled PS-b-P4VP(PDP) supramolecules. The results of the SAXS study on the dependence of the lamellar period of PPE/PS-b-P4VP blends on the amount of PPE were in excellent agreement with a theoretical ...