The purpose of this brief communication is to demonstrate how near infrared (NIR) spectroscopy can be used to study specific interactions in miscible polymer blends. We will first demonstrate, using model systems and blends of polycaprolactone (PCL) and phenoxy [poly(hydroxypropylether of bisphenol-A)], that information obtained from the OH stretch overtone absorption in the NIR is consistent with the information obtained from the OH stretch fundamental in the mid-IR region. We will then illustrate the advantages of NIR analysis of specific interaction with spectra obtained, over a range of temperatures, from thick (2 mm) films of blends of Nylon-6 and the zinc salt of sulfonated polystyrene (ZnSPS).