The blends of poly(hydroxyether of bisphenol A) (phenoxy) with poly(4-vinyl pyridine) (P4VPy) were investigated by differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR) and high-resolution solid-state nuclear magnetic resonance (NMR) spectroscopy. The single, composition-dependent glass transition temperature (T-g) was observed for each blend, indicating that the system is completely miscible. The sigmoid Tg composition relationship is characteristic of the presence of the strong intermolecular specific interactions in the blend system. FTIR studies revealed that there was intermolecular hydrogen bonding in the blends and the intermolecular hydrogen bonding between the pendant hydroxyl groups of phenoxy and nitrogen atoms of pyridine ring is much stronger than that of self-association in phenoxy. To examine the miscibility of the system at the molecular level, the high resolution C-13 cross-polarization (CP)/magic angle spinning (MAS) together with the high-power dipolar decoupling (DD) NMR technique was employed. Upon adding P4VPy to the system, the chemical shift of the hydroxyl-substituted methylene carbon resonance of phenoxy was observed to shift downfield in the C-13 CP/MAS spectra. The proton spin-lattice relaxation time T-1(H) and the proton spin-lattice relaxation time in the rotating frame T-1p(H) were measured as a function of the blend composition. In light of the proton spin-lattice relaxation parameters, it is concluded that the phenoxy and P4VPy chains are intimately mixed on the scale of 20-30 Angstrom.