The chain mobility of a series of hydrogen-bonded polymer complexes and multilayers were compared by variable temperature wide-line deuterium NMR spectroscopy. Poly-(methacrylic add), deuterated at the methyl group, PMAA-d(3), was complexed with five different hydrogen bond acceptor polymers-poly(ethylene oxide) (PEO), poly(acrylamide) (PAAM), poly(vinyl methyl ether) (PVME), poly(vinylpyrrolidone) (PVPon), and poly(vinylcaprolactam) (PVCL)-as well as with chitosan, where the interaction should be primarily ion pairing. The overall chain mobility of PMAA in its water-saturated complexes was observed to increase in the following order: PVCL < PVPon < chitosan < PVME < PAAM < PEO. For these polymer pairs, the same trend in chain mobility was also confirmed for the first few layers deposited on colloidal silica. The observed chain dynamics correlate well with the reported variation of the critical pH, bilayer thickness, and the permeability for multilayer films of the same polymers. In addition, the extent of chain interpenetration was demonstrated through the effect of a stabilizing primer layer on the chain mobility of the subsequently deposited weaker hydrogen-bonded multilayers.