FTIR has been utilized to examine the effect of polymer rigidity and copolymer composition on the accessibility of functional groups to form intermolecular hydrogen bonds in polymer blends. The results illustrate that the accessibility of functional groups to intermolecular hydrogen bonding increases as the distance between these groups along the polymer backbone increases, in agreement with previous studies. The results also demonstrate that an increase in the distance between hydrogen-bonding donating groups also minimizes the importance of the rigidity of the other polymer on the ability to form intermolecular hydrogen bonds. This suggests that in order to form a miscible blend between a rigid and an amorphous polymer, the functional groups that participate in hydrogen bonding should be separated along the backbone polymer chain.