A rare miscible polyacrylonitrile (PAN) blend system is reported. PAN is miscible with poly(p-vinylphenol) (PVPh) as shown by thermal and spectroscopic studies. A single glass transition temperature was found in each blend. Infrared spectroscopic studies showed that the hydroxyl band of PVPh and the cyano band of PAN shifted to lower frequencies upon blending, showing the existence of specific interactions between the two polymers. The involvement of cyano groups in specific interactions was further evidenced by the development of a high-binding-energy N1s peak in each blend from X-ray photoelectron spectroscopic studies.