The role of the main components of a PVAc-based wood adhesive formulation in the formation and performance of the adhesive joint was investigated. A new analytical methodology was applied to carry out the chemical separation and characterization of the adhesive components present in the bond line. By using extraction techniques on the wet and dry glues it was possible to observe the variation in the solubility of the adhesive components, for different glue formulations. The swollen-state NMR technique proved to be a very useful tool to characterize the insoluble parts present in the adhesive films. These findings, when put into relation to some specific properties of the adhesive joints, contribute to the understanding of the mechanisms involved in the adhesion process. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 114: 3841-3854, 2009