The miscibility, intermolecular interactions and thermal behavior of the poly(hydroxy ether of Bisphenol A) (Phenoxy)/poly(ethyl oxazoline) (PEOx) blends were investigated by differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), and high-resolution solid-state nuclear magnetic resonance (NMR) spectroscopy. Each composition of the Phenoxy/PEOx blends investigated displays a single glass transition temperature (Tg), which is intermediate between those of the pure components and regularly varies with blend composition. The results of FTIR showed that there are intermolecular interactions between the pendant hydroxyl groups of Phenoxy and the carbonyl groups of PEOx. Spin-lattice relaxation times in both the laboratory and the rotating frame determined by high-resolution solid state C-13 NMR spectroscopy reveal that the spin-diffusion among all protons in the blends averages out the whole relaxation process, suggesting that the blends are intimately mixed on the scale of 10-15 Angstrom.