A comparative study of three poly(methacrylamides) containing different N-substitutions was carried out in order to obtain a better understanding of the resonance effects on the inter-association and self-association hydrogen bonding interactions in polymer blends. DSC and solid-state NMR analyses are employed to study the relative miscibility of these three binary blends, indicating that the PNPAA/P4VP blend has a better miscibility than the PNMAA/P4VP and PNCHAA/P4VP blends, because the resonance characteristic of the aromatic ring in PNPAA enhances the inter-association hydrogen bonding with P4VP based on FTIR and solid-state NMR analyses.