Novel supramolecular polymer networks were prepared by the reaction of poly(4-vinylpyridine) (P4VP) with 1,5-naphthalenedisulfonic acid (NDS), 1,3-propanedisulfonic acid (PDS), or adipic acid (AA). The IR and XPS analyses of the polymer networks revealed that the P4VP/NDS complex has a higher ionic interaction between pyridinium cation and sulfonate anion than the P4VP/PDS complex, and that hydrogen bonding interaction between pyridine and carboxylic acid predominantly contributes for the P4VP/AA complex. When the glass transition temperatures of P4VP and P4VP/proton donor (1/1) complexes are compared, the higher order was P4VP/NDS > P4VP/PDS > P4VP > P4VP/AA, in agreement with a higher degree of ionic interaction. The P4VP/PDS complex had a melting endothermic peak in the DSC thermograms, which was not observed for the P4VP/NDS complex. The thermal decomposition temperature of the P4VP complexes is also investigated in relation to the intermolecular interaction. (C) 2004 Elsevier Ltd. All rights reserved.