The miscibility and interactions in poly(N-acryloylthiomorpholine) (PATM)/poly(p-vinylphenol) (PVPh) blends were investigated. The PATM/PVPh blends were observed to be transparent and each allowed a single Tg, indicating miscibility. The Fourier transform infrared spectroscopy studies showed the existence of hydrogen-bonding interactions. The X-ray photoelectron spectroscopy (XPS) studies demonstrated that the amide nitrogen atom and sulfur atoms in PATM undergo hydrogen bonding interactions with the hydroxyl groups.